On the determination of molecular weight distributions of asphaltenes and their aggregates in laser desorption ionization experiments

Molecular weight distributions (MWD) of asphaltenes and their aggregates have been investigated in laser desorption ionization (LDI) mass spectrometric experiments. A systematic investigation of the dependence of the measured MWD on the asphaltene sample density and on the laser pulse energy allows the assignment of most probable molecular weights within 300-500 amu and average molecular weights of 800-1000 amu for the monomeric asphaltenes, as well as for the estimation of the contribution from asphaltene clusters in typical LDI measurements. The results serve to reconcile the existing controversy between earlier mass spectrometric characterizations of asphaltenes based on laser desorption techniques by different groups. Furthermore, the MWD measurements performed on particularly dense samples yield an additional differentiated broad band peaking around 9000-10,000 amu and extending over 20,000 amu, not observed previously in LDI experiments, thereby revealing a strong propensity of the asphaltenes to form clusters with specific aggregation numbers, which is in qualitative agreement with previous theoretical predictions and with the interpretation of measurements performed with other techniques.     

Laser desorption/ionization determination of molecular weight distributions of polyaromatic carbonaceous compounds and their aggregates

Molecular weight distributions (MWDs) of model polyaromatic hydrocarbons (PAHs) and complex asphaltene samples have been investigated in laser desorption/ionization mass spectrometry (LDI-MS) experiments. Special efforts are devoted to the characterization of aggregation effects during the desorption process. It is found that non-covalent clusters of the PAHs and asphaltenes form readily in the desorbing plume. Aggregation is favoured in the experiments performed on dense samples at high laser energy and under continuous ion extraction conditions. In the absence of polar groups in the analyte molecules, the aggregation propensity correlates well with the size of the polycondensed system and with its degree of pericondensation, in qualitative agreement with previous theoretical predictions. For the polydispersed asphaltenes from two different crude oils, MWDs peaking at masses smaller than 500 amu with a high-mass tail extending up to about 3000 amu have been observed, yielding average weights around 900 amu. Such MWDs are in good agreement with previous mass spectrometric measurement, as well as with diffusion studies in solution. In addition, stable asphaltene aggregates have been detected giving rise to two broad bands in the mass spectrum corresponding to average molecular weights of 2200-3100 amu and 15,000-19,000 amu, respectively. It is concluded that the strong aggregation propensity of asphaltenes is likely to be responsible for the apparent inconsistency between the MWD for these compounds determined by different groups in independent LDI-MS experiments. The reliability of different sample preparation procedures, including solvent-free methods, is discussed, and strategies are outlined that serve to apply the potentiality of LDI mass spectrometry to the characterization of covalent and non-covalent compounds in complex carbonaceous systems.     

Laser desorption/ionization techniques in the characterization of high molecular weight oil fractions. Part 1: asphaltenes

The molecular weight distribution of the asphaltene fractions of two types of crude oils from two different Italian fields (samples 1 and 2) was investigated. The analytical tools used to perform these analyses were matrix assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) mass spectrometry. After observing that the use of the matrix (as well as the addition of Ag+) did not improve the quality of the data compared to that obtained in LDI conditions, all further measurements were performed with the latter technique. Operating under usual conditions of laser power and delay time, a very low resolution was observed, showing only macroscopic differences between the two samples in the molecular weight distribution of the different components. An accurate study on the possible reasons of this undesirable behavior indicates that it can originate from space charge phenomena occurring either in the ion source region or during the flight. A valid parameterization of the delay time and the laser power allowed higher quality spectra to be obtained. Surface-enhanced laser desorption ionization (SELDI) measurements were also performed using normal phase (silica) as the sample holder surface. Under these conditions, better results are obtained, proving that the sample-surface interaction is important to achieve, by means of laser irradiation, a homogeneous set of product ions. Both asphaltene samples were fractionated in five subfractions by gel-permeation chromatography (GPC) to obtain a better separation of the molecular weight distributions; the related spectra confirmed these findings. By using different approaches, relevant and reproducible differences between the asphaltene fractions of the two oil samples were observed.     

Effect of Asphaltenes and Resins on Asphaltene Aggregation Inhibition,Rheological Behaviour and Waterflood Oil-Recovery

This study presents an investigation about the influence of resins and asphaltenes, extracted from two Mexican crude oils (light and heavy oil samples), on the asphaltene aggregation inhibition, rheological behavior, and waterflood oil-recovery. Resins and asphaltenes were characterized by means of elemental analysis, metals analysis by atomic absorption, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, and electrospray ionization mass spectrometry (ESI-MS) in order to evaluate the effect of their structural parameters on the phenomena studied. Efficiency of the resins fraction as natural inhibitors of asphaltene aggregation was evaluated trough ultraviolet–visible (UV–vis) spectroscopy. Results showed better efficiencies of resins on asphaltene aggregation inhibition at resin/asphaltene (R/A) ratios close to unity and at high temperature. In addition, efficiencies were influenced by structural characteristics of the asphaltene–resin system. Rheological behavior of the heavy crude oil sample was significantly influenced by the presence of asphaltenes and resins. Finally, asphaltenes and resins played an important role on wettability and waterflood oil-recovery.     

Laser desorption ionization and MALDI time-of-flight mass spectrometry for low molecular mass polyethylene analysis

Polyethylene's inert nature and difficulty to dissolve in conventional solvents at room temperature present special problems for sample preparation and ionization in mass spectrometric analysis. We present a study of ionization behavior of several polyethylene samples with molecular masses up to 4000 Da in laser desorption ionization (LDI) time-of-flight mass spectrometers equipped with a 337 nm laser beam. We demonstrate unequivocally that silver or copper ion attachment to saturated polyethylene can occur in the gas phase during the UV LDI process. In LDI spectra of polyethylene with molecular masses above approximately 1000 Da, low mass ions corresponding to metal-alkene structures are observed in addition to the principal distribution. By interrogating a well-characterized polyethylene sample and a long chain alkane, C94H190, these low mass ions are determined to be the fragmentation products of the intact metal-polyethylene adduct ions. It is further illustrated that fragmentation can be reduced by adding matrix molecules to the sample preparation.     

Evaluation of a new matrix-free laser desorption/ionization method through statistic studies: comparison of the DIAMS (desorption/ionization on self-assembled monolayer surface) method with the MALDI and TGFA-LDI techniques

This work demonstrates that the desorption/ionization on self-assembled monolayer surface (DIAMS) mass spectrometry, a recent matrix-free laser desorption/ionization (LDI) method based on an organic target plate, is as statistically repeatable and reproducible as matrix assisted laser desorption ionization (MALDI) and thin gold film-assisted laser desorption/ionization (TGFA-LDI) mass spectrometries. On lipophilic DIAMS of target plates with a mixture of glycerides, repeatability/reproducibility has been estimated at 15 and 30% and the relative detection limit has been evaluated at 0.3 and 3 pmol, with and without NaI respectively. Salicylic acid and its d(6)-isomer analysis confirm the applicability of the DIAMS method in the detection of compounds of low molecular weight.     

Asphaltene aggregation in organic solvents

Asphaltenic solids formed in the Rangely field in the course of a carbon dioxide flood and heptane insolubles in the oil from the same field were used in this study. Four different solvents were used to dissolve the asphaltenes. Near-infrared (NIR) spectroscopy was used to determine the onset of asphaltene precipitation by heptane titration. When the onset values were plotted versus asphaltene concentrations, distinct break points (called critical aggregation concentrations (CAC) in this paper) were observed. CACs for the field asphaltenes dissolved in toluene, trichloroethylene, tetrahydrofuran, and pyridine occurred at concentrations of 3.0, 3.7, 5.0, and 8.2 g/l, respectively. CACs are observed at similar concentrations as critical micelle concentrations (CMC) for the asphaltenes in the solvents employed and can be interpreted to be the points at which rates of asphaltene aggregations change. CMC values of asphaltenes determined from surface tension measurements (in pyridine and TCE) were slightly higher than the CAC values measured by NIR onset measurements. The CAC for heptane-insoluble asphaltenes in toluene was 3.1 g/l. Thermal gravimetric analysis (TGA) and elemental compositions of the two asphaltenes showed that the H/C ratio of the heptane-insoluble asphaltenes was higher and molecular weight (measured by vapor pressure osmometry) was lower.     

Post-source decay of alkylated and functionalized polycyclic aromatic compounds

Post-source decay (PSD) is a valuable tool for providing structural information from large molecules by time-of-flight mass spectrometry (TOFMS). We used PSD to obtain this type of data from small molecules in the laser desorption/ionization (LDI) study of diesel engine exhaust particles. As the original nitrogen laser (lambda = 337 nm, E = 3.5 eV/photon) of our TOF mass spectrometer does not yield sufficient energy to ionize polycyclic aromatic hydrocarbons (PAHs), a second laser with a shorter wavelength has been coupled to the instrument. The fourth harmonic of a Nd:YAG laser (lambda = 266 nm, 4.6 eV/photon) has been chosen to achieve two-photon single-step desorption/ionization of PAHs. The PSD fragmentation of functionalized, alkylated and sulfur PAHs is discussed. Diesel engine exhaust particles are also studied as an example of a real complex sample. This technique is presented herein as a way to identify small molecules in environmental samples. Information provided by LDI-PSD-TOFMS can be a way to distinguish pollutants with very close molecular weights even if the resolving power of a TOF mass spectrometer is not sufficient.     

Laser desorption/ionization mass spectrometric analysis of small molecules using fullerene‐derivatized silica as energy‐absorbing material

In spite of the growing acceptance of matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry for the analysis of a wide variety of compounds, including polymers and proteins, its use in analyzing low‐molecular‐weight molecules (<1000m/z) is still limited. This is mainly due to the interference of matrix molecules in the low‐mass range. Here the derivatized fullerenes covalently bound to silica particles with different pore sizes are applied as thin layer for laser desorption/ionization (LDI) mass spectrometric analysis. Thus, an interference of intrinsic matrix ions can be eliminated or minimized in comparison with the state‐of‐the‐art weak organic acid matrices. The desorption/ionization ability of the developed fullerene–silica materials depends on the applied laser power, sample preparation and pore size of the silica particles. Thus, fullerene–silica serves as an LDI support for mass spectrometric analysis of molecules (<1500 Da). The performance of the fullerene–silica is demonstrated by the mass analysis of variety of small molecules such as carbohydrates, amino acids, peptides, phospholipids and drugs. Copyright © 2010 John Wiley & Sons, Ltd.     

Minimization of Fragmentation and Aggregation by Laser Desorption Laser Ionization Mass Spectrometry

Measuring average quantities in complex mixtures can be challenging for mass spectrometry, as it requires ionization and detection with nearly equivalent cross-section for all components, minimal matrix effect, and suppressed signal from fragments and aggregates. Fragments and aggregates are particularly troublesome for complex mixtures, where they can be incorrectly assigned as parent ions. Here we study fragmentation and aggregation in six aromatic model compounds as well as petroleum asphaltenes (a naturally occurring complex mixture) using two laser-based ionization techniques: surface assisted laser desorption ionization (SALDI), in which a single laser desorbs and ionizes solid analytes; and laser ionization laser desorption mass spectrometry (L²MS), in which desorption and ionization are separated spatially and temporally with independent lasers. Model compounds studied include molecules commonly used as matrices in single laser ionization techniques such as matrix assisted laser desorption ionization (MALDI). We find significant fragmentation and aggregation in SALDI, such that individual fragment and aggregate peaks are typically more intense than the parent peak. These fragment and aggregate peaks are expected in MALDI experiments employing these compounds as matrices. On the other hand, we observe no aggregation and only minimal fragmentation in L²MS. These results highlight some advantages of L²MS for analysis of complex mixtures such as asphaltenes.

纳米材料辅助负离子激光解吸电离-飞行时间质谱分析小分子研究进展

基质辅助激光解吸电离-飞行时间质谱（MALDI-TOF MS）作为一种软电离质谱技术,目前已被广泛用于蛋白质、多肽、核酸、聚合物等大分子分析。由于传统有机化合物基质在低相对分子质量（小于700 Da）区域的干扰,该技术在小分子物质分析方面受到很大限制。为克服传统有机化合物基质在低相对分子质量区域的干扰,近年来以纳米材料为代表的无机基质材料备受关注。相对传统有机化合物基质或纳米材料正离子模式,基于纳米材料的负离子激光解吸电离（LDI）有效避免了正离子模式下一种化合物会产生多种加合物的问题,具有图谱简单易于解析、灵敏度高、重现性好等优点。该文综述了近5年来纳米材料负离子LDI-TOF MS技术在小分子分析方面的研究进展,以期拓展该技术在小分子分析方面的应用。     

Approaches for the analysis of low molecular weight compounds with laser desorption/ionization techniques and mass spectrometry

This review summarizes various approaches for the analysis of low molecular weight (LMW) compounds by different laser desorption/ionization mass spectrometry techniques (LDI-MS). It is common to use an agent to assist the ionization, and small molecules are normally difficult to analyze by, e.g., matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) using the common matrices available today, because the latter are generally small organic compounds themselves. This often results in severe suppression of analyte peaks, or interference of the matrix and analyte signals in the low mass region. However, intrinsic properties of several LDI techniques such as high sensitivity, low sample consumption, high tolerance towards salts and solid particles, and rapid analysis have stimulated scientists to develop methods to circumvent matrix-related issues in the analysis of LMW molecules. Recent developments within this field as well as historical considerations and future prospects are presented in this review.     

Molecular representation of coal-derived asphaltene based on high resolution mass spectrometry

The asphaltene separated by solubility in small molecular alkanes and toluene is the most structurally diverse and complex components in heavy oil, such as vacuum residue and coal tar. The coal-derived asphaltene is always regard as a succession of maltene fraction from small molecules to large molecules, and also a continuum of island- and archipelago-type structures, which is difficult to be identified accurately through current characterization methods. This limits the further study of molecular dynamics and reaction dynamics simulation of asphaltenes. In this work, a representation model of molecular composition and structure for coal-derived asphaltene is developed mainly based on Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with collision induced dissociation (CID) and traditional methods of nuclear magnetic resonance spectroscopy (¹³C NMR), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS). Island- and archipelago-type structures are considered qualitatively in the representation of asphaltene. The asphaltene molecules are systematic assembled using stochastic algorithms and optimized by simulated annealing algorithm according to the group contribution method. The bulk properties for simulating asphaltenes are in good agreement with the experimental results giving acceptable predictions for the composition and structure of the asphaltenes. Moreover, the representative average structure asphaltene molecules are obtained using the developed molecular similarity function, which could be applied in the further study of molecular aggregation simulation and reaction kinetics simulation.     

Matrix-free and material-enhanced laser desorption/ionization mass spectrometry for the analysis of low molecular weight compounds

The application of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) for the analysis of low molecular weight (LMW) compounds, such as pharmacologically active constituents or metabolites, is usually hampered by employing conventional MALDI matrices owing to interferences caused by matrix molecules below 700 Da. As a consequence, interpretation of mass spectra remains challenging, although matrix suppression can be achieved under certain conditions. Unlike the conventional MALDI methods which usually suffer from background signals, matrix-free techniques have become more and more popular for the analysis of LMW compounds. In this review we describe recently introduced materials for laser desorption/ionization (LDI) as alternatives to conventionally applied MALDI matrices. In particular, we want to highlight a new method for LDI which is referred to as matrix-free material-enhanced LDI (MELDI). In matrix-free MELDI it could be clearly shown, that besides chemical functionalities, the material’s morphology plays a crucial role regarding energy-transfer capabilities. Therefore, it is of great interest to also investigate parameters such as particle size and porosity to study their impact on the LDI process. Especially nanomaterials such as diamond-like carbon, C₆₀ fullerenes and nanoparticulate silica beads were found to be excellent energy-absorbing materials in matrix-free MELDI.     

硅纳米结构对表面辅助激光解吸/电离质谱检测性能的提高

本文总结了多种构筑硅纳米结构的方法, 综述了近年来利用硅纳米结构提高表面辅助激光解吸/电离质谱(SALDI-MS)性能的研究工作, 展望了利用功能化的硅纳米结构表面进一步提高激光解吸/电离(LDI)效率的前景.     

Probing the molecular weight distributions of non-boiling petroleum fractions by Ag+ electrospray ionization mass spectrometry

This work explores the possibility of Ag+ electrospray ionization mass spectrometry (ESI-MS) to determine the molecular weight distributions of non-boiling petroleum fractions. Information about the molecular weight distributions is needed for fundamental studies on the nature of heavy crude oils and bitumens and for the development of novel recovery and processing methods. The method does not depend on thermal processes for the introduction of the fractions into the gas phase of the mass spectrometer, which is a considerable advantage over most other ionization methods. The Ag+ electrospray mass spectra of the fractions analyzed by using a toluene/methanol/cyclohexane (60:28:12%) solvent system display bimodal distributions in the ranges m/z approximately 300 to approximately 3000 and m/z 3000 to approximately 20,000. The abundances of the high molecular weight peak distributions can be reduced by in-source collisional activation experiments. Comparisons with the results obtained for model heteroatom-containing compounds (molecular weight < 600 Da) and high molecular weight polystyrene standards (up to one million Da) indicate that the majority of the structures in the saturate, naphthenoaromatic and polar aromatic fractions, and a significant portion of the asphaltenes, are small molecules. However, a considerable portion of the asphaltenes and some portion of the other fractions contain high molecular weight structures bound by covalent or strong non-covalent bonds. The results obtained by the Ag+ ESI method in this study for the saturate, aromatic, and polar fractions in a bitumen are in qualitative agreement with published molecular weight average results obtained for Cold Lake bitumen fractions analyzed by conventional gel permeation chromatography and field desorption mass spectrometry. Further work is needed to study the nature of the bonds and the interactions of the molecules in the asphaltene fractions by Ag+ ESI-MS.     

The use of nonpolar matrices for matrix-assisted laser desorption/ionization mass spectrometric analysis of high boiling crude oil fractions

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) with nonpolar matrices has been investigated for its applicability to the characterization of atmospheric resid crude oil fractions. The data obtained by use of nonpolar matrices was compared with that from polar matrices as well as from direct LDI-MS and field ionization mass spectrometry. Nonpolar matrices, such as anthracene or 9-cyanoanthracene, yield only a single radical molecular cation upon LDI. Thus, no interfering matrix-related ions are present during the MALDI-TOFMS analysis of the crude oil sample. Nonpolar matrices yield molecular mass distributions from linear mode MALDI-TOFMS that are comparable to distributions found with LDI-MS. An advantage of nonpolar matrices is the increased production of analyte ions, which allows reflectron mode MALDI-TOFMS to be performed. Nonpolar matrices are also shown to be less sensitive to solvent and sample preparation conditions than conventional polar matrices. These results suggest that nonpolar matrices may be favorable alternatives to more traditional polar or acidic matrices commonly used in the MALDI mass spectral characterization of crude oil related samples.     

Compressibilities and excess surface areas of mixed asphaltene/resin monolayers. Influence of demulsifiers.

Compressibilities (C_s) and excess surface areas (ΔA_M) are calculated for mixed films of asphaltenes and resins and asphaltenes combined with different commercial demulsifiers from Langmuir measurements. Both attraction and repulsion is observed between asphaltenes and resins, depending on the composition of the film. High molecular weight demulsifiers present in an asphaltene film increase the compressibility and the repulsion in the film, which is important for the demulsification process of water and crude oil emulsions.     

Evaluation of matrix-assisted laser desorption ionization mass spectrometry for polymer characterization

A protocol for the preparation of polymeric samples for time-of-flight matrix-assisted laser desorption ionization mass spectrometry (TOF-MALDI-MS) analysis was developed. Dithranol was identified as a good matrix for polystyrene (PS), and the addition of silver for cationization of molecules was determined to be necessary. Based on this preparative method, low molecular weight samples of other polymers [polyisoprene, polybutadiene, poly(ethylene oxide), poly(methyl methacrylate), and polydimethylsiloxane] were analyzed with molecular weights up to 49 ku. The effects of laser intensity were determined to influence the molecular weight distribution of intact oligomers, most significantly for low molecular weight polymers. Linear and reflectron modes of analysis were evaluated; better signal intensity and resolution were obtained in the reflectron mode. The TOF-MALDI-MS measurements are compared with time-of-flight secondary ion mass spectrometry (TOF-SIMS) and gel permeation chromatography (GPC) for the same polymers. The M _n values calculated by TOF-MALDI-MS consistently are higher than values calculated by TOF-SIMS for all classes of polymers with molecular weights up to 8 ku. The molecular weights of the PS calculated from TOF-MALDI-MS are in good agreement with GPC (±10%). The composition of the terminal group on a polymer chain may affect the ion yields. The ion yields of intact oligomers were evaluated as a function of end group composition for both TOF-MALDI-MS and TOF-SIMS. The slight disparity of results between TOF-SIMS and TOF-MALDI-MS for the perfluoroalkyl-terminated PS suggests that the oligomers are desorbed preferentially from the surface in the TOF-SIMS analysis, rather than having an increased ionization probability.     

Online aerosol mass spectrometry of single micrometer-sized particles containing poly(ethylene glycol)

The analysis of poly(ethylene glycol) (PEG)-containing particles by online single particle aerosol mass spectrometers equipped with laser desorption/ionization (LDI) is reported. We demonstrate that PEG-containing particles are useful in the development of aerosol mass spectrometers because of their ease of preparation, low cost, and inherently recognizable mass spectra. Solutions containing millimolar quantities of PEGs were nebulized and, after drying, the resultant micrometer-sized PEG-containing particles were sampled. LDI (266 nm) of particles containing NaCl and PEG molecules of average molecular weight<500 Da generated mass spectra reminiscent of mass spectra of PEG collected by other mass spectrometer platforms including the characteristic distribution of positive ions (Na+ adducts) separated by the 44 m/z units of the ethylene oxide units separating each degree of polymerization. PEGs of average molecular weight>500 Da were detected from particles that also contained the tripeptide tyrosine-tyrosine-tyrosine or 2,5-dihydroxybenzoic acid, which were added to nebulized solutions to act as matrices to assist LDI using pulsed 266 nm and 355 nm lasers, respectively. Experiments were performed on two aerosol mass spectrometers, one reflectron and one linear, that each utilize two time-of-flight mass analyzers to detect positive and negative ions created from a single particle. PEG-containing particles are currently being employed in the optimization of our bioaerosol mass spectrometers for the application of measurements of complex biological samples, including human effluents, and we recommend that the same strategies will be of great utility to the development of any online aerosol LDI mass spectrometer platform.