We describe a simple gas expansion ion source based on static discharge voltages and a commercially available pulsed valve. The discharge is initiated by the gas pulse itself between two high voltage electrodes, without the need for fast voltage switches or complex timing schemes. The ion source very reliably produces intense bursts of molecular ions (with currents exceeding 100 μA during the pulse-on phase) with only minor pulse-to-pulse variations in intensity and pulse shape.
View Article and Find Full Text PDFWe show that strong molecular rotation drastically modifies the autodetachment of C_{2}^{-} ions in the lowest quartet electronic state a^{4}Σ_{u}^{+}. In the strong-rotation regime, levels of this state only decay by a process termed "rotationally assisted" autodetachment, whose theoretical description is worked out based on the nonlocal resonance model. For autodetachment linked with the exchange of six rotational quanta, the results reproduce a prominent, hitherto unexplained electron emission signal with a mean decay time near 3 ms, observed on stored C_{2}^{-} ions from a hot ion source.
View Article and Find Full Text PDF6-Nitrobenzo[]thiophene 1,1-dioxide (Stattic) is a potent signal transducer and activator of the transcription 3 (STAT3) inhibitor developed originally for anticancer therapy. However, Stattic harbors several STAT3 inhibition-independent biological effects. To improve the properties of Stattic, we prepared a series of analogues derived from 6-aminobenzo[]thiophene 1,1-dioxide, a compound directly obtained from the reduction of Stattic, that includes a methoxybenzylamino derivative (K2071) with optimized physicochemical characteristics, including the ability to cross the blood-brain barrier.
View Article and Find Full Text PDFWe present a merged-beams study of reactions between HD^{+} ions, stored in the Cryogenic Storage Ring (CSR), and laser-produced ground-term C atoms. The molecular ions are stored for up to 20 s in the extreme vacuum of the CSR, where they have time to relax radiatively until they reach their vibrational ground state (within 0.5 s of storage) and rotational states with J≤3 (after 5 s).
View Article and Find Full Text PDFFood Addit Contam Part A Chem Anal Control Expo Risk Assess
January 2024
A call for data on the occurrence of alkylfurans in food and feed from EFSA triggered the development of new methods to cover next to furan also 2- and 3-methylfuran, 2,5-dimethyl- and 2-ethylfuran as well as 2-pentylfuran. A significant variability was noticed when comparing analysis of 2-pentylfuran and furans in the same matrix performed by different laboratories. To assess the variability an interlaboratory study including eight laboratories was organised.
View Article and Find Full Text PDFA low-cost Digital Signal Processor (DSP) unit for advanced Scanning Probe Microscopy measurements is presented. It is based on Red Pitaya board and custom built electronic boards with additional high bit depth AD and DA converters. By providing all the necessary information (position and time) with each data point collected it can be used for any scan path, using either existing libraries for scan path generation or creating adaptive scan paths using Lua scripting interface.
View Article and Find Full Text PDFWhile the dissociative recombination (DR) of ground-state molecular ions with low-energy free electrons is generally known to be exothermic, it has been predicted to be endothermic for a class of transition-metal oxide ions. To understand this unusual case, the electron recombination of titanium oxide ions (TiO) with electrons has been experimentally investigated using the Cryogenic Storage Ring. In its low radiation field, the TiO ions relax internally to low rotational excitation (≲100 K).
View Article and Find Full Text PDFHigh-resolution micro- and nanostructures can be grown using Focused Electron Beam Induced Deposition (FEBID), a direct-write, resist-free nanolithography technology which allows additive patterning, typically with sub-100 nm lateral resolution, and down to 10 nm in optimal conditions. This technique has been used to grow magnetic tips for use in Magnetic Force Microscopy (MFM). Due to their high aspect ratio and good magnetic behavior, these FEBID magnetic tips provide several advantages over commercial magnetic tips when used for simultaneous topographical and magnetic measurements.
View Article and Find Full Text PDFSignal transducer and activator of transcription 3 (STAT3) signalling serves an important role in carcinogenesis and cellular senescence, and its inhibition in tumour cells represents an attractive therapeutic target. Premature cellular senescence, a process of permanent proliferative arrest of cells in response to various inducers, such as cytostatic drugs or ionizing radiation, is accompanied by morphological and secretory changes, and by altered susceptibility to chemotherapeutic agents, which can thereby complicate their eradication by cancer therapies. In the present study, the responsiveness of proliferating and docetaxel (DTX)‑induced senescent cancer cells to small molecule STAT3 inhibitor Stattic and its analogues was evaluated using tumour cell lines.
View Article and Find Full Text PDFTo date, the most studied drug in anti-aging research is the mTOR inhibitor - rapamycin. Despite its almost perfect anti-aging profile, rapamycin exerts one significant limitation - inappropriate physicochemical properties. Therefore, we have decided to utilize virtual high-throughput screening and fragment-based design in search of novel mTOR inhibiting scaffolds with suitable physicochemical parameters.
View Article and Find Full Text PDFFor sensitive studies of molecular ions in electrostatic storage rings, the exact knowledge of the isobaric composition of stored beams from a variety of ion sources is essential. Conventional mass-filtering techniques are often inefficient to resolve the beam components. Here, we report the first isochronous mass spectrometry in an electrostatic storage ring, which offers a high mass resolution of Δm/m < 1 × 10 even for heavy molecular species with m > 100 u and uncooled ion beams.
View Article and Find Full Text PDFWe present state-selected measurements of rotational cooling and excitation rates of CH^{+} molecular ions by inelastic electron collisions. The experiments are carried out at a cryogenic storage ring, making use of a monoenergetic electron beam at matched velocity in combination with state-sensitive laser dissociation of the CH^{+} ions for simultaneous monitoring of the rotational level populations. Employing storage times of up to 600 s, we create conditions where electron-induced cooling to the J=0 ground state dominates over radiative relaxation, allowing for the experimental determination of inelastic electron collision rates to benchmark state-of-the-art theoretical calculations.
View Article and Find Full Text PDFPhosphatidic acid (PA), an important signalling and metabolic phospholipid, is predominantly localized in the subapical plasma membrane (PM) of growing pollen tubes. PA can be produced from structural phospholipids by phospholipase D (PLD), but the isoforms responsible for production of PM PA were not identified yet and their functional roles remain unknown. Following genome-wide bioinformatic analysis of the PLD family in tobacco, we focused on the pollen-overrepresented PLDδ class.
View Article and Find Full Text PDFCheeses are a group of fermented dairy products that are produced all over the world in various forms and flavours. Milk, especially sheep or goat milk, is still regarded as an expensive raw material in the world, which makes milk and milk products highly attractive as a fraud target. Most often, such fraud includes partial or complete substitution with cheaper sorts of milk (e.
View Article and Find Full Text PDFPhilos Trans A Math Phys Eng Sci
September 2019
The new Cryogenic Storage Ring at the Max Planck Institute for Nuclear Physics (Heidelberg, Germany) has recently become operational. One of the main research areas foreseen for this unique facility is astrochemical studies with cold molecular ions. The spontaneous radiative cooling of the prototype interstellar molecule CH to its lowest rotational states has been demonstrated by photodissociation spectroscopy, paving the way for experiments under true interstellar conditions.
View Article and Find Full Text PDFThe epoch of first star formation in the early Universe was dominated by simple atomic and molecular species consisting mainly of two elements: hydrogen and helium. Gaining insight into this constitutive era requires a thorough understanding of molecular reactivity under primordial conditions. We used a cryogenic ion storage ring combined with a merged electron beam to measure state-specific rate coefficients of dissociative recombination, a process by which electrons destroy molecular ions.
View Article and Find Full Text PDFThe generation of selected Maillard-derived odorants from iso-oligosaccharides (IOSs), namely, from isomaltose, isomaltotriose, isomaltulose, and melibiose, was studied and compared with that from other oligosaccharides (maltose, lactose, and panose) and monosaccharides (glucose, galactose, and fructose). The study was carried out in binary mixtures of sugar and amino acids (glycine, proline, and cysteine) and upon wafer baking. The results indicate that IOSs induce browning and generation of the majority of the monitored odorants, in particular 4-hydroxy-2,5-dimethyl-3(2 H)-furanone, 2,3-butanedione, 2-acetyl-1-pyrroline, 2-propionyl-1-pyrroline, 2-acetylthiazole, and 2-acetyl-2-thiazoline, far more than the other oligosaccharides and to a higher or similar degree to that of the monosaccharides.
View Article and Find Full Text PDFPhotodetachment thermometry on a beam of OH^{-} in a cryogenic storage ring cooled to below 10 K is carried out using two-dimensional frequency- and time-dependent photodetachment spectroscopy over 20 min of ion storage. In equilibrium with the low-level blackbody field, we find an effective radiative temperature near 15 K with about 90% of all ions in the rotational ground state. We measure the J=1 natural lifetime (about 193 s) and determine the OH^{-} rotational transition dipole moment with 1.
View Article and Find Full Text PDFAn electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.
View Article and Find Full Text PDFWe have studied the photodissociation of CH^{+} in the Cryogenic Storage Ring at ambient temperatures below 10 K. Owing to the extremely high vacuum of the cryogenic environment, we were able to store CH^{+} beams with a kinetic energy of ∼60 keV for several minutes. Using a pulsed laser, we observed Feshbach-type near-threshold photodissociation resonances for the rotational levels J=0-2 of CH^{+}, exclusively.
View Article and Find Full Text PDFA compact, highly efficient single-particle counting detector for ions of keV/u kinetic energy, movable by a long-stroke mechanical translation stage, has been developed at the Max-Planck-Institut für Kernphysik (Max Planck Institute for Nuclear Physics, MPIK). Both, detector and translation mechanics, can operate at ambient temperatures down to ∼10 K and consist fully of ultra-high vacuum compatible, high-temperature bakeable, and non-magnetic materials. The set-up is designed to meet the technical demands of MPIK's Cryogenic Storage Ring.
View Article and Find Full Text PDFThe absolute configuration of (R,R)-2,3-dideuterooxirane, which has been independently determined using Coulomb explosion imaging, has been unambiguously chemically correlated with the stereochemical key reference (+)-glyceraldehyde. This puts the absolute configuration of D(+)-glyceraldehyde on firm experimental grounds.
View Article and Find Full Text PDFIn chemistry and biology, chirality, or handedness, refers to molecules that exist in two spatial configurations that are incongruent mirror images of one another. Almost all biologically active molecules are chiral, and the correct determination of their absolute configuration is essential for the understanding and the development of processes involving chiral molecules. Anomalous x-ray diffraction and vibrational optical activity measurements are broadly used to determine absolute configurations of solid or liquid samples.
View Article and Find Full Text PDFThe formation pathways of the N-containing roast-smelling compounds 2-acetyl-1-pyrroline, 2-acetyl-1(or 3),4,5,6-tetrahydropyridine, and their structural analogues 2-propionyl-1-pyrroline and 2-propionyl-1(or 3),4,5,6-tetrahydropyridine were studied upon extrusion cooking using the CAMOLA approach. The samples were produced under moderate extrusion conditions (135 °C, 20% moisture, 400 rpm) employing a rice-based model recipe enriched with flavor precursors ([U-(13)C6]-D-glucose, D-glucose, glycine, L-proline, and L-ornithine). The obtained data indicate that the formation of these compounds upon extrusion follows pathways similar to those reported for nonsheared model systems containing D-glucose and L-proline.
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