Investigating the Kinetics of Heterogeneous Lipid Ozonolysis by an Online Photoionization High-Resolution Mass Spectrometry Technique.

Lipid oxidation-induced imbalance in the redox system is one of the key causative factors leading to accelerated aging in living organisms and related diseases. Online sampling and analysis of the heterogeneous ozonolysis kinetics of lipid aerosols are highly important in revealing the oxidation-driven aging process of lipids. In this paper, an online detection method based on atmospheric pressure photoionization combined with ultrahigh resolution mass spectrometry (APPI-HRMS) is developed for real-time analysis of the heterogeneous reactions between lipid particles (oleic acid and squalene) and ozone.

Guidelines for Identifying the Structure of Heavy Phenolics in Lignin Depolymerization by using High-Resolution Tandem Mass Spectrometry.

The efficient conversion of lignin contributes to reducing human reliance on fossil energy. As a complicated biopolymer, studies on the mechanism of lignin depolymerization is limited by inadequate structural identification of high molecular weight (MW) products like heavy phenolics. Up to now, no individual method can generate both MW and structural information in operando conditions.

Online Compositional Analysis of Complex Oligomers in Biomass Degradation by High-Pressure Flow-Through Reactor Coupled with High-Resolution Mass Spectrometry.

Online analysis of the composition and evolution of complex oligomeric intermediates in biomass degradation is highly desirable to elucidate the mechanism of bond cleavage and study the effect of conditions on the selective conversion of feedstocks. However, harsh reaction conditions and complicated conversion systems pose tremendous challenges for conventional, state-of-the-art analytical techniques. Herein, we introduce a continuous and rapid compositional analysis strategy coupling a high-pressure flow-through reactor with online high-resolution mass spectrometry, which enables the molecular-level characterization of most biomass-related products throughout the conversion for over 2 h.

AP-HTPB propellant combustion under strain conditions with laser absorption spectroscopy.

Understanding the combustion behaviors of solid propellant with different levels of strains is of practical interest. In this work, an experimental study of the effects of static and dynamic strains on the burning rate, temperature, CO, and formation of aluminized ammonium perchlorate (AP)-hydroxyl terminated poly-butadiene (HTPB) propellant combustion was presented at initial pressures of 0.1 MPa, 0.

Role of formaldehyde in promoting aromatic selectivity during methanol conversion over gallium-modified zeolites.

Gallium-modified HZSM-5 zeolites are known to increase aromatic selectivity in methanol conversion. However, there are still disputes about the exact active sites and the aromatic formation mechanisms over Ga-modified zeolites. In this work, in situ synchrotron radiation photoionization mass spectrometry (SR-PIMS) experiments were carried out to study the behaviors of intermediates and products during methanol conversion over Ga-modified HZSM-5.

A Mechanistic Study of HZSM-5-Catalyzed Guaiacol Amination Using Photoionization Time-of-Flight Mass Spectrometry.

Thermal-catalytic conversion and amination (TCC-A) of lignin and lignin derivates over zeolites is a promising and renewable method to produce aromatic amines, but suffers from product diversity. Currently, no unambiguous mechanism could fully describe the chemistry of this process. In this work, the TCC-A mechanism of guaiacol, a typical lignin model compound, with ammonia over HZSM-5 was investigated by online photoionization time-of-flight mass spectrometry combined with density functional theory.

Probing combustion and catalysis intermediates by synchrotron vacuum ultraviolet photoionization molecular-beam mass spectrometry: recent progress and future opportunities.

Soft photoionization molecular-beam mass spectrometry (PI-MBMS) using synchrotron vacuum ultraviolet (SVUV) light has been significantly developed and applied in various fields in recent decades. Particularly, the tunability of SVUV light enables two-dimensional measurements, mass spectrum and photoionization efficiency spectrum measurements, affording isomer distinguishment in complex reaction processes. Many key intermediates have been successfully detected in combustion and catalysis reactions with the help of the state-of-the-art SVUV-PI-MBMS, promoting the understanding of the chemical mechanisms.

In Situ Reactor-Integrated Electrospray Ionization Mass Spectrometry for Heterogeneous Catalytic Reactions and Its Application in the Process Analysis of High-Pressure Liquid-Phase Lignin Depolymerization.

Process analysis of heterogeneous catalytic reactions such as lignin depolymerization is essential to understand the reaction mechanism at the molecular level, but it is always challenging due to harsh conditions. Herein, we report an operando process analysis strategy by combining a microbatch reactor with high-resolution mass spectrometry (MS) via a reactor-integrated electrospray ionization (R-ESI) technique. R-ESI-MS expands the applications of traditional in situ MS to a heterogeneous and high-pressure liquid-phase system.

Continuous Butadiyne Addition to Propargyl: A Radical-Efficient Pathway for Polycyclic Aromatic Hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) play a crucial role in soot inception, interstellar evolution, and nanomaterial synthesis. Although several mechanisms, such as hydrogen-abstraction acetylene/vinylacetylene addition, have previously been proposed, PAH formation and growth are not yet fully understood. We propose an alternate PAH growth mechanism wherein propargyl radical reacts with butadiyne to form larger radicals containing newly fused aromatic rings.

Online investigation on catalytic co-pyrolysis of cellulose and polyethylene over magnesium oxide by advanced mass spectrometry.

Due to rapid deactivation of catalysts, the effective conversion of biomass with oxygen-rich and hydrogen-deficient characteristics to transportation fuels and high-valued chemicals via catalytic pyrolysis remains a challenge for commercialization. Hydrogen-rich plastic is used as feedstock co-fed with biomass to improve the catalytic pyrolysis process. The present work aims to investigate the co-pyrolysis process of cellulose and polyethylene (PE) over MgO by TG combined with photoionization time-of-flight mass spectrometry (PI-TOF-MS), which features on-line detection of catalytic pyrolysis products in real time.

Insights into the Decomposition and Oxidation Chemistry of -Xylene in Laminar Premixed Flames.

This work reports an experimental and kinetic modeling investigation on laminar premixed flame of -xylene at 0.04 atm and equivalence ratios of 0.75, 1.

Evidence of a Phenolic Pool as a Key Intermediate for Zeolite-Catalyzed Lignin Pyrolysis.

The phenolic pool is considered to be an important intermediate during the catalytic conversion of biomass. However, no direct evidence has been reported on its full picture on a molecular level due to the huge challenges in probing the reactive and lowly volatile phenolic oligomers with state-of-the-art technologies. Herein, we report the online detection and structural identification of a phenolic pool by utilizing in-situ atmospheric-pressure photoionization mass spectrometry, demonstrating that the phenolic pool is formed through repolymerization of monomers with an equidistant group pattern and acts as a key mechanistic step for both valuable aromatic products and undesired coke.

Study of the thermal decomposition mechanism of FOX-7 by molecular dynamics simulation and online photoionization mass spectrometry.

The thermal decomposition mechanism of energetic materials is important for analyzing the combustion mechanisms of propellants and evaluating the safety of propellants during transport and storage. 1,1-Diamino-2,2-dinitroethylene (FOX-7) is an important insensitive energetic material that can be used as an oxidizer in propellants. However, the initial decomposition mechanism of FOX-7 is not clear to date.

Formation and Fate of Formaldehyde in Methanol-to-Hydrocarbon Reaction: In Situ Synchrotron Radiation Photoionization Mass Spectrometry Study.

HCHO has been confirmed as an active intermediate in the methanol-to-hydrocarbon (MTH) reaction, and is critical for interpreting the mechanisms of coke formation. Here, HCHO was detected and quantified during the MTH process over HSAPO-34 and HZSM-5 by in situ synchrotron radiation photoionization mass spectrometry. Compared with conventional methods, excellent time-resolved profiles were obtained to study the formation and fate of HCHO, and other products during the induction, steady-state reaction, and deactivation periods.

In Situ Atmospheric Pressure Photoionization Mass Spectrometric Monitoring of Initial Pyrolysis Products of Biomass in Real Time.

Knowledge on the initial and intermediate pyrolysis products of biomass is essential for the mechanistic investigation of biomass pyrolysis and further optimization of upgrading processes. The conventional method can only detect the final products, which do not resemble the initial or intermediate pyrolysis products. Here, we introduce a direct orifice sampling combined with atmospheric pressure photoionization mass spectrometry (APPI-MS) for in situ online analysis of the evolved volatile initial products from the pyrolysis of biomass.

Online photoionization mass spectrometric evaluation of catalytic co-pyrolysis of cellulose and polyethylene over HZSM-5.

The hydrogen-deficient and oxygen-rich nature of lignocellulosic biomass prohibits effective conversions of biomass to fuels and chemicals via catalytic pyrolysis due to significant coking of the catalysts. Co-feeding of biomass feedstock with hydrogen-rich and oxygen-deficient thermoplastics could improve the process. Herein, thermal and catalytic co-pyrolysis of cellulose and polyethylene (PE) was studied via thermogravimetry combined with an online photoionization time-of-flight mass spectrometry (PI-TOF-MS).

Note: Possibilities of detecting the trace-level erosion products from an electric propulsion hollow cathode plasma source by the method of time-of-flight mass spectrometry.

A hollow cathode produces electrons which neutralize ions from electric propulsion thrusters. After hundreds to thousands of hours of operation in space, the cathode materials can be significantly eroded due to ion bombardment. As a result, the electric propulsion system performance will be obviously changed or even fail.

Extractive Atmospheric Pressure Photoionization (EAPPI) Mass Spectrometry: Rapid Analysis of Chemicals in Complex Matrices.

Extractive atmospheric pressure photoionization (EAPPI) mass spectrometry was designed for rapid qualitative and quantitative analysis of chemicals in complex matrices. In this method, an ultrasonic nebulization system was applied to sample extraction, nebulization, and vaporization. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by a high resolution time-of-flight mass spectrometer (TOF-MS).

The vacuum ultraviolet beamline/endstations at NSRL dedicated to combustion research.

An undulator-based vacuum ultraviolet (VUV) beamline (BL03U), intended for combustion chemistry studies, has been constructed at the National Synchrotron Radiation Laboratory (NSRL) in Hefei, China. The beamline is connected to the newly upgraded Hefei Light Source (HLS II), and could deliver photons in the 5-21 eV range, with a photon flux of 10(13) photons s(-1) at 10 eV when the beam current is 300 mA. The monochromator of the beamline is equipped with two gratings (200 lines mm(-1) and 400 lines mm(-1)) and its resolving power is 3900 at 7.

Selective conversion of syngas to light olefins.

Although considerable progress has been made in direct synthesis gas (syngas) conversion to light olefins (C2(=)-C4(=)) via Fischer-Tropsch synthesis (FTS), the wide product distribution remains a challenge, with a theoretical limit of only 58% for C2-C4 hydrocarbons. We present a process that reaches C2(=)-C4(=) selectivity as high as 80% and C2-C4 94% at carbon monoxide (CO) conversion of 17%. This is enabled by a bifunctional catalyst affording two types of active sites with complementary properties.

Ultrasonic nebulization extraction/low pressure photoionization mass spectrometry for direct analysis of chemicals in matrices.

A novel ultrasonic nebulization extraction/low-pressure photoionization (UNE-LPPI) system has been designed and employed for the rapid mass spectrometric analysis of chemicals in matrices. An ultrasonic nebulizer was used to extract the chemicals in solid sample and nebulize the solvent in the nebulization cell. Aerosols formed by ultrasonic were evaporated by passing through a transferring tube, and desolvated chemicals were ionized by the emitted light (10.

A field-programmable-gate-array based time digitizer for the time-of-flight mass spectrometry.

The time-of-flight (TOF) mass spectrometry is one of the most widely used techniques to get information about the composition and structure of compounds. The time digitizer, based on time-to-digital conversion, is one of the important parts in modern TOF mass spectrometry, which is often implemented with analog circuitry or application-specific-integrated-circuit (ASIC) devices. However, it is difficult to achieve a high density with the analog approach.

On-line product analysis of pine wood pyrolysis using synchrotron vacuum ultraviolet photoionization mass spectrometry.

The pyrolysis process of pine wood, a promising biofuel feedstock, has been studied with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry. The mass spectra at different photon energies and temperatures as well as time-dependent profiles of several selected species during pine wood pyrolysis process were measured. Based on the relative contents of three lignin subunits, the data indicate that pine wood is typical of softwood.

Note: Laser-induced acoustic desorption∕synchrotron vacuum ultraviolet photoionization mass spectrometry for analysis of fragile compounds and heavy oils.

In this work, we coupled synchrotron vacuum ultraviolet photoionization (SVUV PI) method with the laser-induced acoustic desorption (LIAD) technique for mass spectrometric analysis. The LIAD technique is a "soft" desorption method, which could avoid the degradation of analytes during desorption process. Meanwhile, SVUV PI is an efficient "soft" ionization source.

NEW EXPERIMENTAL EVIDENCES ABOUT THE FORMATION AND CONSUMPTION OF KETOHYDROPEROXIDES.

The formation of hydroperoxides postulated in all the kinetic models for the low temperature oxidation of alkanes have been experimentally proved thanks to a new type of apparatus associating a quartz jet-stirred reactor through a molecular-beam sampling system to a reflectron time-of-flight mass spectrometer combined with tunable synchrotron vacuum ultraviolet photoionization. This apparatus has been used to investigate the low-temperature oxidation of -butane and has allowed demonstrating the formation of different types of alkylhydroperoxides, namely methylhydroperoxide, ethylhydroperoxide and butylhydroperoxide, and of C alkylhydroperoxides including a carbonyl function (ketohydroperoxides). In addition, the formation of products deriving from these ketohydroperoxides, such as C molecules including either two carbonyl groups or one carbonyl and one alcohol functions, has been observed.