European Journal of Mass Spectrometry最新文献

The dimer and trimer structures of the non-amyloidogenic rat islet amyloid polypeptide 21-37 peptide, formed in an H₂O/CH₃OH (1% CH₃COOH) solution were investigated using electrospray ionization-tandem mass spectrometry (ESI-MS/MS). The dissociation of monomers, dimers, and trimers was investigated by MS/MS using collision-induced dissociation. The peptide bond dissociation between L₇ and P₈ was mainly observed in the tandem mass spectra of the monomers and oligomers, regardless of the parent ion charge state. The fragment ions were observed as a series of b_u (u = 3-4, 6-7, 12) or y_n (n = 10-11, 13-14) in the [Mono + 2H]²⁺ (=[monomer + 2H]²⁺) tandem mass spectrum. MS/MS analysis of the [Di + 3H]³⁺ (=[dimer + 3H]³⁺) complex indicated that [Di + 3H]³⁺ comprised [Mono + H]¹⁺ and [Mono + 2H]²⁺ subunits. During covalent bond dissociation of the [Di + 3H]³⁺ complex, a fragmentation pattern was observed in the form of {mono + (fragment ion of [Mono + 2H]²⁺)}, resulting from the collision energy dissociation of the [Mono + 2H]²⁺ peptide. The [(C-terminal)-(C-terminal)] interaction geometry was proposed for the [Di + 3H]³⁺ complex based on the observation of [y₁₀+ y_n]²⁺ (n = 10-11, 13-16) fragment ions in the [Di + 3H]³⁺ tandem mass spectrum. MS/MS analysis of the [Tri + 4H]⁴⁺ (=[trimer + 4H]⁴⁺) complex indicated that [Tri + 4H]⁴⁺ comprised [Mono + H]¹⁺ and [Di + 3H]³⁺ subunits. The (monomer-[Di + 3H]³⁺)⁴⁺ complex geometry was assumed to be stable based on the presence of {mono + (fragment ion of [Di + 3H]³⁺)} ions in the tandem mass spectrum of the [Tri + 4H]⁴⁺ complex. The two [Mono + (y₁₀+ y₁₀)]²⁺ and [Mono + (Mono + y₁₀)]³⁺ fragment ions also supported the (monomer-[Di + 3H]³⁺)⁴⁺ complex geometries of the [Tri + 4H]⁴⁺ complex. The [(C-terminal)-(C-terminal)] interaction geometry of the [Di + 3H]³⁺ subunit is thought to be conserved in the [Tri + 4H]⁴⁺ complex geometries.

Gels created by self-assembly of small organic molecules are dynamic soft materials that have unique properties and demanding characterization. Four chiral gelators, with two valinol- or leucinoloxamido arms attached to the 2,2'-positions of the proatropisomeric biphenyl group were chosen to show that the electrospray ionization mass spectrometry (ESI-MS) could be used to differentiate the gelation feature of the chiral compounds 1-4 and also to shed light on the gelation processes. By inspecting the gelation of several solvents, we showed that 1 (R, R) proved to be the most efficient gelator, forming the largest observable assemblies in the gas phase. The strong intermolecular H-bonds hold single-charged assemblies consisting of up to five monomer units detectable by ESI MS. Enantiomer 1 (R, R) is a good gelator due to favorable intramolecular interactions that remain preserved in the gas phase. Compound 3 (meso) does not have gelator properties and detected signals of larger assemblies in the gas phase. So, the detected signals correlate with the conformations of the studied compounds. MS could be used to elucidate the preferential type of noncovalent interaction due to the chiral recognition. The study paves a novel way to investigate the influence of chirality on the molecular assembly and consequently macroscopic properties and functions of materials.

This article presents a relationship between the size of an ion crystal in a Paul trap and the radio frequency potential applied on the central ring electrode. Using a simple and elegant derivation it has been shown that the distance of an ion in the crystal from the trap center is proportional to $-2/3$ power of the applied radio frequency voltage. The validity of this power law has been demonstrated on ion crystals having up to 13 ions. A spring-mass model has been presented to predict structure of ion crystals in Paul traps operating in the Dehmelt regime. Structures are obtained by minimizing the total potential energy stored in an ion ensemble. The total potential energy is taken to be the sum of the electrostatic potential due to ion-ion interaction and the potential energy stored in the springs. Structures of crystals having up to 13 ions predicted by our model have been verified by comparing them with results obtained by direct numerical simulations.

Present work describes the development of a liquid chromatography tandem mass spectrometry-based bioanalytical method for the reliable simultaneous quantification of docetaxel (DXL) and carvacrol (CVL) in the mice plasma. A rapid and sensitive bioanalytical method was developed and optimized in mice plasma using Paclitaxel as an internal standard. Validation of the bioanalytical method was performed according to the ICH M10 guideline covering the range of 9.62-1923.08 ng/mL in the mice plasma milleu at the low, mid, and high-quality control concentrations of 28.86 ng/mL, 961.54 ng/mL, and 1346.15 ng/mL, respectively for both the analytes. Validation parameters such as accuracy, precision, carryover-test, matrix effect, and reinjection reproducibility were carried out and were found in limits. Stability studies (Benchtop, autosampler, freeze-thaw, and long-term) were performed and found to be within limits. The developed bioanalytical method was found to be suitable for the simultaneous quantification of DXL and CVL in the mice plasma.

Mass spectrometry (MS) has become a pivotal analytical tool across various scientific disciplines due to its ability to provide detailed molecular information with high sensitivity and specificity. MS plays a crucial role in various fields, including drug discovery and development, proteomics, metabolomics, environmental analysis, and clinical diagnostics and Forensic science. In this article we are discussing the application of MS across the diverse scientific disciplines by focusing on some classical examples from each field of application. As the technology continues to evolve, it promises to unlock new possibilities in scientific research and practical applications, cementing its position as an essential tool in modern analytical science.

Exenatide is a synthetic glucagon-like peptide 1 analog, widely used in the management of type 2 diabetes mellitus. The stability of pharmaceutical products is significantly impacted by various environmental stress conditions. The present study reports the development of a validated reverse-phase high-performance liquid chromatography (RP-HPLC) stability-indicating method for the identification of force degradation products (DPs) of synthetic glucagon-like peptide-1 analog Exenatide using UHPLC-Orbitrap fusion^TM mass spectrometer. Force degradation studies were performed by subjecting Exenatide to various stress conditions, such as hydrolytic, oxidative, photolytic and thermal to investigate the stability indicating ability of the method. Significant degradation was observed during acidic, oxidative, photolytic and thermal stress conditions. Exenatide and its major DPs identification and characterization were demonstrated by employing LC-HRMS and MS/MS method. In total, five major stress DPs were characterized, and their fragmentation pathway was proposed using MS/MS studies. Finally, the proposed RP-HPLC method was validated as per ICH guidance.

We consider the operation of a digital linear ion trap with resonance radial ejection and mass selective instability modes. Periodic wave shape has a positive part with amplitude $V^{+}=V_0$ and duration $0.8T$ and negative part with amplitude $V^{-}=-4V_0$ and duration $0.2T$, where T is the period. The mapping of the stability diagram, calculations of the well's depth and ion oscillations spectra are presented. The process of resonant excitation of ion oscillations by a dipole sinusoidal signal is studied, as well as ion ejection at the stability boundary. The trajectory method is used for this purpose. It is shown that the mass selectivity of dipole excitation is twice as large for rectangular wave shape compared to sinusoidal wave shape. Increasing the diameter of the round rods of the linear trap gives an increase in the resolving power. The possibility of DIT operation in mass-selective instability mode at the boundary point $q_b=0.39$ is discussed.

This paper proposed a dual-layer linear ion trap mass analyzer (dLIT) based on micro-electromechanical systems (MEMS) technology and stacked-layer structure for the development of MEMS mass spectrometry. Its basic performance and potential capabilities were explored by ion trajectory simulations. The theoretical formulas were modified by implementing multipole expansion. The simulation results were confirmed to be highly consistent with theoretical calculations in multiple aspects, including stability diagram, secular frequencies, and mass linearity, with only a deviation of 1-2%. In the boundary ejection mode, close to 100% ejection was achieved in a single dimension by applying extra quadrupole DC voltage. Preliminary simulation results showed that dLIT can achieve a peak width of ∼2 mass units (full width at half maximum, FWHM) for m/z 60 ions even at pressures as high as 50 Pa. Furthermore, the application of AC frequency scanning mode in dLIT was also evaluated, and preliminary simulation results yield a peak width of 0.3-0.4 mass units (FWHM). The dLIT offered several advantages, including high-precision fabrication at the sub-millimeter scale, excellent high-pressure performance, and a clear physical model. It preliminarily proved to be an ideal mass analyzer for MEMS mass spectrometry.

Thermal decomposition and isomerization of 1-butyl and 1-pentyl radical were studied in the temperature range of 500-1480 K on a short time scale of 20-100 µs using flash pyrolysis vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry. 1-Bromobutane and 1-bromopentane were used as precursors for the 1-butyl and 1-pentyl radical, respectively. The reactive intermediates in the thermal dissociation reactions were directly observed. The 1-butyl radical decomposed to ethene and ethyl radical with ethyl radical rapidly losing an H atom to form a second ethene molecule. Loss of H atom from butyl radical was also a significant decomposition channel. Isomerization of 1-butyl via 1,3-H migration was observed as a minor channel at 1380 K and above with a branching ratio of less than 3% at 1430 K. The 1-pentyl radical was observed to decompose mainly by isomerization to 2-pentyl radical followed by β-scission to produce propene and ethyl radicals at temperatures approximately 900 K and below. Above 900 K, β-scission of 1-pentyl to produce ethene and 1-propyl radical became increasingly important. Isomerization to 3-pentyl was verified to be a minor channel.

This paper presents a newly developed high-performance mobile single-photon ionization time-of-flight mass spectrometry (M-SPI-TOFMS) system for on-line analysis and stereoscopic monitoring of complex gas mixtures. The system is designed for stereoscopic imaging to map the distribution of volatile organic compounds (VOCs) and trace their emission sources in urban areas and industrial parks. It mainly consists of a SPI-TOFMS instrument, a customized commercial vehicle, a meteorological five-parameter monitor with GPS, a high-power generator, and an uninterruptible power supply. The SPI technique, using a 118 nm VUV lamp, can ionize compounds with an ionization potential below 10.78 eV. Mass spectra obtained using this technique show the profiles of various VOCs and some inorganic compounds. The VOCs composition information and mobile location data are simultaneously sent to the GIS software. In GIS software, this data is used for real-time stereoscopic imaging of VOC distribution and precise tracking of VOC movement. The system can achieve a spatial data resolution of 0.69 mm at 25 km/h due to the microsecond detection speed of the M-SPI-TOFMS instrument. The laboratory test provides a rapid overview characterization of benzene, toluene, and xylene. The M-SPI-TOFMS has limits of detection and mass resolution of 33.7 pptv and 1060, respectively. Several field applications were carried out using M-SPI-TOFMS at various locations to identify VOC sources near different factories. The M-SPI-TOFMS system has a navigation monitoring speed of 25 km/h with a time resolution of 1 s. The widespread use of this system will provide accurate data to support environmental management departments in formulating VOCs pollution control policies and improving control efficiency.