Photoionization and photofragmentation in mass spectrometry with visible and UV lasers.

Ever since the introduction of laser technology to the field of mass spectrometry, several disciplines evolved providing solutions to challenging scientific and analytical tasks in research and industry. Among these are techniques involving multiphoton ionization such as Resonance-Enhanced Multiphoton Ionization (REMPI, R2PI) and Mass-Analyzed Threshold Ionization (MATI) spectroscopy, a variant of Zero Kinetic Energy (ZEKE) spectroscopy, that possess the ability to selectively ionize certain preselected compounds out of complex mixtures, for example, environmental matrices, with a high level of efficiency. Another key feature of multiphoton ionization techniques is the ability to control the degree of fragmentation, whereas soft ionization is most highly appreciated in most applications. In cases where rich fragmentation patterns are desired for diagnostic purposes, Photodissociation mass spectrometry (PD-MS) is applied successfully. PD-MS allows for the cleavage of selected chemical bonds. With the introduction of chromophoric labels in PD-MS, it became possible to target certain molecules or groups within a molecule. In this review article, an overview of the basic principles and experimental requirements of REMPI and MATI spectroscopy and PD mass spectrometry are given. By means of selected examples, the latest developments and application possibilities in this field over the past decade with special focus on the German research landscape are pointed out. © 2018 Wiley Periodicals, Inc. Mass Spec Rev 38: 202-217, 2019.

Analysis of the (1)A' S1 ← (1)A' S0 and (2)A' D0 ← (1)A' S1 band systems in 1,2-dichloro-4-fluorobenzene by means of resonance-enhanced-multi-photon-ionization (REMPI) and mass-analyzed-threshold-ionization (MATI) spectroscopy.

Resonance enhanced multiphoton ionization (REMPI) and mass analyzed threshold ionization (MATI) spectroscopy have been applied in order to investigate the vibrational structure of 1,2-dichloro-4-fluorobenzene (1,2,4-DCFB) in its first excited state (S1) and the cationic ground state (D0). The selection of the state prior to ionization resulted in MATI spectra with different intensity distributions thus giving access to many vibrational levels. To support the experimental findings, geometry optimizations and frequency analyses at DFT (density functional) and TDDFT (time-dependent density functional) levels of theory have been applied. Additionally, a multidimensional Franck-Condon approach has been used to calculate the vibrational intensities from the DFT calculations. An excellent agreement between simulated and measured REMPI and MATI spectra allowed for a confident assignment of vibrational levels and mechanisms active during excitation and ionization. In order to avoid any ambiguity regarding the assignment of the vibrational bands to normal modes, Duschinsky normal mode analysis has been performed to correlate the ground state (S0) normal modes of 1,2,4-DCFB with the benzene derived Wilson nomenclature. From the REMPI spectra the electronic excitation energy (EE) of 1,2-dichloro-4-fluorobenzene could be determined to be 35 714 ± 2 cm(-1) while the MATI spectra yielded the adiabatic ionization energy (IE) of 1,2-dichloro-4-fluorobenzene which could be determined to be 73 332 ± 7 cm(-1).

A Highly Triflated Rare-Earth Ion in [Eu(O3SCF3)8](5-).

The reaction of Eu2O3 with fuming nitric acid, trifluormethanesulfonic acid, and its anhydride in torch-sealed glass ampoules at 120 °C gave the europium compound (NO)5[Eu(O3SCF3)8] (orthorhombic, Fddd, Z = 16, a = 1932.69(4), b = 2878.44(7), c = 2955.12(7) pm, V = 16439.7(7) Å(3)). The compound exhibits the [Eu(O3SCF3)8](5-) anion showing for the first time a lanthanide ion that is exclusively coordinated by eight triflate anions. The anion has been further investigated by DFT calculations, which also allowed clear assignment of the vibrational spectra. Moreover, magnetochemical and luminescence measurements gave additional insight into the properties of this complex. The luminescence spectra revealed that the Eu(3+) ions are in a pseudo D4d symmetric environment.

Magnetic resonance-guided cardiac interventions using magnetic resonance-compatible devices: a preclinical study and first-in-man congenital interventions.

BACKGROUND: Percutaneous cardiac interventions are currently performed under x-ray guidance. Magnetic resonance imaging (MRI) has been used to guide intravascular interventions in the past, but mainly in animals. Translation of MR-guided interventions into humans has been limited by the lack of MR-compatible and safe equipment, such as MR guide wires with mechanical characteristics similar to standard guide wires. The aim of the present study was to evaluate the safety and efficacy of a newly developed MR-safe and compatible passive guide wire in aiding MR-guided cardiac interventions in a swine model and describe the 2 first-in-man solely MR-guided interventions. METHODS AND RESULTS: In the preclinical trial, the new MR-compatible wire aided the performance of 20 interventions in 5 swine. These consisted of balloon dilation of nondiseased pulmonary and aortic valves, aortic arch, and branch pulmonary arteries. After ethics and regulatory authority approval, the 2 first-in-man MR-guided interventions were performed in a child and an adult, both with elements of valvar pulmonary stenosis. Catheter manipulations were monitored with real-time MRI sequence with interactive modification of imaging plane and slice position. Temporal resolution was 11 to 12 frames/s. Catheterization procedure times were 110 and 80 minutes, respectively. Both patients had successful relief of the valvar stenosis and no procedural complications. CONCLUSIONS: The described preclinical study and case reports are encouraging that with the availability of the new MR-compatible and safe guide wire, certain percutaneous cardiac interventions will become feasible to perform solely under MR guidance in the future. A clinical trial is underway in our institution.

Magnetic resonance imaging of the cardiac venous system and magnetic resonance-guided intubation of the coronary sinus in swine: a feasibility study.

OBJECTIVES: To visualize the coronary sinus using magnetic resonance (MR), and to demonstrate the feasibility of MR-guided intubation of the cardiac venous system (CVS) in swine. MATERIALS AND METHODS: A total of 6 pigs were investigated. All experiments were performed using an interventional 1.5-Tesla MRI system. The CVS was visualized using an inversion-recovery navigator-gated whole-heart steady-state free-precession sequence after administration of gadobenate dimeglumine contrast agent. The coronary sinus was then intubated under MR-guidance with a passive MR-compatible guidewire modified by incorporation of iron oxide markers for improved visualization and a nonbraided Cobra-catheter. MR-guided interventions were monitored using a steady-state free-precession real-time imaging sequence. Time needed was measured for MR-guided intubation of the CVS and compared with the time needed for fluoroscopy guided intubation of the CVS. RESULTS: Visualization and intubation of the coronary sinus and its site branches was feasible in all cases. Time spent for MR-guided intubation of the CVS was comparable to time spent for fluoroscopy-guided intubation (8.2 +/- 2 minutes vs. 8.3 +/- 1.3 minutes; P = 0.85). CONCLUSIONS: MR-visualization and MR-guided intubation of the coronary sinus and its side branches is feasible. The feasibility of MR-guided intubation of the CVS might have relevance for procedures like cardiac resynchronization therapy and percutaneous transcatheter mitral annuloplasty, requiring improved 3-dimensional knowledge about cardiac vein anatomy in the near future.

Rapid right ventricular pacing with MR-compatible pacemaker lead for MR-guided aortic balloon valvuloplasty in swine.

PURPOSE: To assess the feasibility and effectiveness of rapid right ventricular pacing with a magnetic resonance (MR)-compatible pacemaker lead during MR-guided aortic valvuloplasty. MATERIALS AND METHODS: This study was approved by the institutional animal research committee. Seven pigs were investigated. All experiments were performed with an interventional 1.5-T MR system. Interventions were monitored with a steady-state free precession real-time imaging sequence. An MR-compatible pacemaker lead was placed in the right ventricular apex with MR guidance before valvuloplasty. After positioning the balloon in valve position, valvuloplasty was performed with rapid right ventricular rapid pacing at a heart rate of 180 beats per minute to minimize cardiac output. RESULTS: Positioning of the pacemaker lead with MR guidance was feasible in all swine (sensing, 6 mV +/- 1; threshold, 1 V +/- 0.5). The lead could be seen on steady-state free precession images without inducing any artifacts. Rapid right ventricular pacing was feasible in all swine, and balloon stability at the time of inflation was achieved with no balloon movement. Aortic valvuloplasty was successfully accomplished in all experiments. CONCLUSION: Rapid right ventricular pacing with an MR-compatible pacemaker lead is feasible and effective.

Preclinical evaluation of a novel fiber compound MR guidewire in vivo.

PURPOSE: Interventional magnetic resonance imaging requires dedicated and MR-compatible devices. The guidewire is a key item for intravascular interventions. Mechanical stability, good visibility during real-time imaging, and RF safety are essential. A novel fiber-compound MR guidewire (GW) was evaluated in different MR-guided interventional scenarios. MATERIALS AND METHODS: The GW (diameter 0.032") consists of a fiber-compound produced using a micropultrusion technique doped with iron particles and a 10-cm Nitinol tip. Several iron splints are additionally attached at regular distances to visualize GW-movement. A protective polymer jacket with hydrophilic coating covers the core material. As approved by the government committee on animal investigations, the GW was evaluated in 5 pigs. Under complete MR-guidance, catheterization of the carotid and renal arteries, segmental arteries of the kidneys, the contralateral inguinal artery, and the left ventricle was performed using real-time gradient echo sequences in a 1.5 Tesla scanner. Different interventional applications including balloon dilatation, stent deployment, and embolization of small vessels were investigated. The time to probe the vessels under magnetic resonance imaging guidance and visibility of the GW are assessed. Handling and visibility under fluoroscopy were compared with a standard Nitinol guidewire as a benchmark. RESULTS: On real-time magnetic resonance imaging, the iron-induced artifacts enabled a distinct visualization of the GW shaft and of its markings with a mean size of 2.6 mm and 5.4 mm, respectively. This facilitated fast navigation to the target vessels (averages: renal arteries 16 seconds, carotid artery 5 seconds, and contralateral inguinal artery 42 seconds.) with an exact depiction of the respective vessel. All interventional procedures were performed successfully. No GW-related side effects as kinking or breakage of the wire or GW induced blood-clotting were observed. All interventionalists assessed handling of the GW to be nearly equal in terms of stiffness, flexibility, and guidance compared with a standard Nitinol guidewire. X-ray visibility was less distinct but still diagnostically good. CONCLUSION: With the aid of the GW, different fully real-time MR-guided endovascular interventions become feasible.