Photophysics of indole upon x-ray absorption

A photofragmentation study of gas-phase indole (C$_8$H$_7$N) upon single-photon ionization at a photon energy of 420 eV is presented. Indole was primarily inner-shell ionized at its nitrogen and carbon $1s$ orbitals. Electrons and ions were measured in coincidence by means of velocity map imaging. The angular relationship between ionic fragments is discussed along with the possibility to use the angle-resolved coincidence detection to perform experiments on molecules that are strongly oriented in their recoil-frame. The coincident measurement of electrons and ions revealed fragmentation-pathway-dependent electron spectra, linking the structural fragmentation dynamics to different electronic excitations. Evidence for photoelectron-impact self-ionization was observed.Comment: 11 pages, 6 figure

High-repetition-rate and high-photon-flux 70 eV high-harmonic source for coincidence ion imaging of gas-phase molecules

Unraveling and controlling chemical dynamics requires techniques to image structural changes of molecules with femtosecond temporal and picometer spatial resolution. Ultrashort-pulse x-ray free-electron lasers have significantly advanced the field by enabling advanced pump-probe schemes. There is an increasing interest in using table-top photon sources enabled by high-harmonic generation of ultrashort-pulse lasers for such studies. We present a novel high-harmonic source driven by a 100 kHz fiber laser system, which delivers 10$^{11}$ photons/s in a single 1.3 eV bandwidth harmonic at 68.6 eV. The combination of record-high photon flux and high repetition rate paves the way for time-resolved studies of the dissociation dynamics of inner-shell ionized molecules in a coincidence detection scheme. First coincidence measurements on CH$_3$I are shown and it is outlined how the anticipated advancement of fiber laser technology and improved sample delivery will, in the next step, allow pump-probe studies of ultrafast molecular dynamics with table-top XUV-photon sources. These table-top sources can provide significantly higher repetition rates than the currently operating free-electron lasers and they offer very high temporal resolution due to the intrinsically small timing jitter between pump and probe pulses

Growth independent rhamnolipid production from glucose using the non-pathogenic Pseudomonas putida KT2440

<p>Abstract</p> <p>Background</p> <p>Rhamnolipids are potent biosurfactants with high potential for industrial applications. However, rhamnolipids are currently produced with the opportunistic pathogen <it>Pseudomonas aeruginosa </it>during growth on hydrophobic substrates such as plant oils. The heterologous production of rhamnolipids entails two essential advantages: Disconnecting the rhamnolipid biosynthesis from the complex quorum sensing regulation and the opportunity of avoiding pathogenic production strains, in particular <it>P. aeruginosa</it>. In addition, separation of rhamnolipids from fatty acids is difficult and hence costly.</p> <p>Results</p> <p>Here, the metabolic engineering of a rhamnolipid producing <it>Pseudomonas putida </it>KT2440, a strain certified as safety strain using glucose as carbon source to avoid cumbersome product purification, is reported. Notably, <it>P. putida </it>KT2440 features almost no changes in growth rate and lag-phase in the presence of high concentrations of rhamnolipids (> 90 g/L) in contrast to the industrially important bacteria <it>Bacillus subtilis, Corynebacterium glutamicum</it>, and <it>Escherichia coli. P. putida </it>KT2440 expressing the <it>rhlAB</it>-genes from <it>P. aeruginosa </it>PAO1 produces mono-rhamnolipids of <it>P. aeruginosa </it>PAO1 type (mainly C₁₀:C₁₀). The metabolic network was optimized in silico for rhamnolipid synthesis from glucose. In addition, a first genetic optimization, the removal of polyhydroxyalkanoate formation as competing pathway, was implemented. The final strain had production rates in the range of <it>P. aeruginosa </it>PAO1 at yields of about 0.15 g/g_glucosecorresponding to 32% of the theoretical optimum. What's more, rhamnolipid production was independent from biomass formation, a trait that can be exploited for high rhamnolipid production without high biomass formation.</p> <p>Conclusions</p> <p>A functional alternative to the pathogenic rhamnolipid producer <it>P. aeruginosa </it>was constructed and characterized. <it>P. putida </it>KT24C1 pVLT31_<it>rhlAB </it>featured the highest yield and titer reported from heterologous rhamnolipid producers with glucose as carbon source. Notably, rhamnolipid production was uncoupled from biomass formation, which allows optimal distribution of resources towards rhamnolipid synthesis. The results are discussed in the context of rational strain engineering by using the concepts of synthetic biology like chassis cells and orthogonality, thereby avoiding the complex regulatory programs of rhamnolipid production existing in the natural producer <it>P. aeruginosa</it>.</p

Alignment, orientation, and Coulomb explosion of difluoroiodobenzene studied with the pixel imaging mass spectrometry (PImMS) camera

Citation: Amini, K., Boll, R., Lauer, A., Burt, M., Lee, J. W. L., Christensen, L., . . . Rolles, D. (2017). Alignment, orientation, and Coulomb explosion of difluoroiodobenzene studied with the pixel imaging mass spectrometry (PImMS) camera. Journal of Chemical Physics, 147(1). doi:10.1063/1.4982220Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C6H3F2I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths. © 2017 Author(s)

Jitter-correction for IR/UV-XUV pump-probe experiments at the FLASH free-electron laser

In pump-probe experiments employing a free-electron laser (FEL) in combination with a synchronized optical femtosecond laser, the arrival-time jitter between the FEL pulse and the optical laser pulse often severely limits the temporal resolution that can be achieved. Here, we present a pump-probe experiment on the UV-induced dissociation of 2,6-difluoroiodobenzene (C6H3F2I) molecules performed at the FLASH FEL that takes advantage of recent upgrades of the FLASH timing and synchronization system to obtain high-quality data that are not limited by the FEL arrival-time jitter. We discuss in detail the necessary data analysis steps and describe the origin of the time-dependent effects in the yields and kinetic energies of the fragment ions that we observe in the experiment

Rapid sample delivery for megahertz serial crystallography at X-ray FELs

Liquid microjets are a common means of delivering protein crystals to the focus of X-ray free-electron lasers (FELs) for serial femtosecond crystallography measurements. The high X-ray intensity in the focus initiates an explosion of the microjet and sample. With the advent of X-ray FELs with megahertz rates, the typical velocities of these jets must be increased significantly in order to replenish the damaged material in time for the subsequent measurement with the next X-ray pulse. This work reports the results of a megahertz serial diffraction experiment at the FLASH FEL facility using 4.3 nm radiation. The operation of gas-dynamic nozzles that produce liquid microjets with velocities greater than 80 m s-1 was demonstrated. Furthermore, this article provides optical images of X-ray-induced explosions together with Bragg diffraction from protein microcrystals exposed to trains of X-ray pulses repeating at rates of up to 4.5 MHz. The results indicate the feasibility for megahertz serial crystallography measurements with hard X-rays and give guidance for the design of such experiments

Trace elements at the intersection of marine biological and geochemical evolution

Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages has yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies

Three galactic globular cluster candidates

‘In these times, during the rise in the popularity of institutional repositories, the Society does not forbid authors from depositing their work in such repositories. However, the AAS regards the deposit of scholarly work in such repositories to be a decision of the individual scholar, as long as the individual's actions respect the diligence of the journals and their reviewers.’ Original article can be found at : http://iopscience.iop.org/ Copyright American Astronomical SocietyContext. The census of Galactic globular clusters (GCs) is still incomplete, and about ten new objects are supposed to await discovery, hidden behind the crowded and reddened regions of the Galactic bulge and disk. Aims. We investigated the nature of three new GC candidates, discovered in the frames collected by the Vista Variables in the Via Lactea (VVV) near-infrared survey. They will be called VVV CL002, VVV CL003, and VVV CL004. Methods. We studied the results of point-spread-function near-infrared photometry from VVV data for the three objects and their surrounding fields, the proper motion information available in the literature and, when possible, we derived the cluster parameters by means of calibrated indices measured on the color-magnitude diagrams. Results. The evidence shows that VVV CL002 is a newly discovered, small, moderately metal-rich ([Fe/H] ∼-0.4) Galactic GC. It is located at a Galactocentric distance of 0.7 ± 0.9 kpc, and it could be one of the nearest GC to the Galactic center. Its characteristics are more similar to those of low-mass, Palomar-like GCs than to more classical, old, and massive bulge GCs. VVV CL003 is the first star cluster discovered in the Galactic disk on the opposite side of the center with respect to the Sun, at a Galactocentric distance of ∼5 kpc. Its high metallicity ([Fe/H] ≈-0.1) and location point to an open cluster, but a GC cannot be excluded. VVV CL004, on the contrary, is most probably only a random clump of field stars, as indicated by both its low statistical significance and by the impossibility to distinguish its stars from the surrounding field population. Conclusions. We claim the detection of i) a new Galactic GC, deriving an estimate of its basic parameters; ii) a stellar aggregate, probably an open cluster, in the disk directly beyond the Galactic center; and iii) an overdensity of stars, most probably an asterism.Peer reviewedFinal Accepted Versio