Laser-plasma interaction in the context of inertial fusion: experiments and modeling

Many nonlinear processes may affect the laser beam propagation and the laser energy deposition in the underdense plasma surrounding the pellet. These processes, associated with anomalous and nonlinear absorption mechanisms, are fundamental issues in the context of Inertial Confinement Fusion. The work presented in this article refers to laser-plasma interaction experiments which were conducted under well-controlled conditions, and to their theoretical and numerical modeling. Thanks to important diagnostics improvements, the plasma and laser parameters were sufficiently characterized in these experiments to make it possible to carry out numerical simulations modeling the laser plasma interaction in which the hydrodynamics conditions were very close to the experimental ones. Two sets of experiments were carried out with the LULI 2000 and the six beam LULI laser facilities. In the first series of experiments, the interaction between two single hot spots was studied as a function of their distance, intensity and light polarization. In the second series, the intensity distribution of stimulated Brillouin scattering (SBS) inside the plasma was studied by means of a new temporally resolved imaging system. Two-dimensional (2D) simulations were carried out with our code Harmony2D in order to model these experiments. For both series of experiments, the numerical results show a very good agreement with the experimental ones for what concerns the main SBS features, namely the spatial and temporal behavior of the SBS-driven acoustic waves, as well as the average SBS reflectivities. Thus, these well diagnosed experiments, carried out with well defined conditions, make it possible to benchmark our theoretical and numerical modelings and, hence, to improve our predictive capabilities for future experiments.     

The chemical etching of fission fragment tracks in natural fluorite

An experimental study of the mechanism for chemical etching of fission fragment tracks in the natural mineral fluorite is described. A systematic search showed that a 3:1 mixture by volume of sulphuric to hydrochloric acids was a most appropriate etchant. Experiments directed at determining the etching efficiency as a function of solvent temperature are also discussed. The preferential track etch ratioVt/Vg, the track length and the track density all depend upon the time and temperature of annealing.

It is variations of the fission track density in fluorite, with etching time and annealing temperature, which make possible an overall geophysical interpretation of annealing data for the mineral in terms of the paleoisotherm of its intrinsic fission track clock.

An interactive image analysis system INTIMAN, assembled for the swift and automatic readout of fission fragment track measurements, in both crystalline and non-crystalline materials, is described. Normal procedures for measuring and analyzing tracks are outlined.     

Plasma Photocathodes

Plasma wakefield accelerators offer accelerating and focusing electric fields three to four orders of magnitude larger than state-of-the-art radiofrequency cavity-based accelerators. Plasma photocathodes can release ultracold electron populations within such plasma waves and thus open a path toward tunable production of well-defined, compact electron beams with normalized emittance and brightness many orders of magnitude better than state-of-the-art. Such beams will have far-reaching impact for applications such as light sources, but also open up new vistas on high energy and high field physics. This paper reviews the innovation of plasma photocathodes, and reports on the experimental progress, challenges, and future prospects of the approach. Details of the proof-of-concept demonstration of a plasma photocathode in 90° geometry at SLAC FACET within the E-210: Trojan Horse program are described. Using this experience, alongside theoretical and simulation-supported advances, an outlook is given on future realizations of plasma photocathodes such as the upcoming E-310: Trojan Horse-II program at FACET-II with prospects toward excellent witness beam parameter quality, tunability, and stability. Future installations of plasma photocathodes also at compact, hybrid plasma wakefield accelerators, will then boost capacities and open up novel capabilities for experiments at the forefront of interaction of high brightness electron and photon beams.     

A novel approach to quantitative LC-MS/MS: therapeutic drug monitoring of clozapine and norclozapine using isotopic internal calibration

Therapeutic drug monitoring (TDM) requires timely results in order to be clinically helpful. Such assays, when carried out using mass spectrometry-based methods, typically involve a batched sample approach with multipoint calibration. Isotopic internal calibration offers the possibility of open-access mass spectrometric analysis with consequent shortening of turnaround times. We measured plasma clozapine and N-desmethylclozapine (norclozapine) concentrations in (1) external quality assessment (EQA) samples (N?=?22) and (2) patient samples (N?=?100) using liquid chromatography-tandem mass spectrometry with isotopic internal calibration (ICAL-LC-MS/MS). Analyte concentrations were calculated from graphs of the response of three internal calibrators (clozapine-D₄, norclozapine-D₈, and clozapine-D₈) against concentration. Precision (% RSD) and accuracy (% nominal concentrations) for the ICAL-LC-MS/MS method were <5 % and 104–112 %, respectively for both analytes. There was excellent agreement with consensus mean and with ‘spiked’ values on analysis of the EQA samples (R ²?=?0.98 and 0.97, respectively, inclusive of clozapine and norclozapine results). In the patient samples, comparison against traditionally calibrated HPLC-UV and LC-MS/MS methods showed excellent agreement (R ²?=?0.97 or better) with small albeit significant mean differences (<0.041 and <0.042 mg/L for clozapine and norclozapine, respectively). These differences probably reflect discrepancies in the in-house preparation of calibrators and/or interference in the UV method. Internal calibration offers a novel and attractive alternative to traditionally calibrated batch analysis in analytical toxicology. The method described has been validated for use in the high-throughput TDM of clozapine and norclozapine, and allows for (1) same-day reporting of results and (2) significant cost savings.

Conformational Isomerism in Monomeric,Low‐Coordinate Group 12 Complexes Stabilized by a Naphthyl‐Substituted m‐Terphenyl Ligand

The synthesis and characterization of the first series of low‐coordinate bis(terphenyl) complexes of the Group 12 metals, [Zn(2,6‐Naph₂C₆H₃)₂] ( 1 ), [Cd(OEt₂)(2,6‐Naph₂C₆H₃)₂] ( 2 ) and [Hg(OEt₂)(2,6‐Naph₂C₆H₃)₂] ( 3 ) (Naph=1‐C₁₀H₇) are described. The naphthyl substituents of the terphenyl ligands confer considerable steric bulk, and as a result of limited flexibility introduce multiple conformations to these unusual systems. In the solid state, complex 1 features a two‐coordinate Zn centre with the ligands oriented in a syn/anti conformation, whereas the three‐coordinate distorted T‐shaped complexes 2 and 3 feature the ligands in the syn/syn configurations. The results of DFT calculations are in good agreement with the solid‐state configurations for these complexes and support the spectroscopic measurements, which indicate several conformers in solution.     

Lateral Metallation and Redistribution Reactions of Sodium Ferrates Containing Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilide Ligands

Alkali-metal ferrates containing amide groups have emerged as regioselective bases capable of promoting Fe−H exchanges of aromatic substrates. Advancing this area of heterobimetallic chemistry, a new series of sodium ferrates is introduced incorporating the bulky arylsilyl amido ligand N(SiMe₃)(Dipp) (Dipp=2,6-iPr₂-C₆H₃). Influenced by the large steric demands imposed by this amide, transamination of [NaFe(HMDS)₃] (HMDS=N(SiMe₃)₂) with an excess of HN(SiMe₃)(Dipp) led to the isolation of heteroleptic [Na(HMDS)₂Fe{N(SiMe₃)Dipp}]_∞ ( 1 ) resulting from the exchange of just one HMDS group. An alternative co-complexation approach, combining the homometallic metal amides [NaN(SiMe₃)Dipp] and [Fe{N(SiMe₃)Dipp}₂] induces lateral metallation of one Me arm from the SiMe₃ group in the iron amide furnishing tetrameric [NaFe{N(SiCH₂Me₂)Dipp}{N(SiMe₃)Dipp}]₄ ( 2 ). Reactivity studies support that this deprotonation is driven by the steric incompatibility of the single metal amides rather than the basic capability of the sodium reagent. Displaying synergistic reactivity, heteroleptic sodium ferrate 1 can selectively promote ferration of pentafluorobenzene using one of its HMDS arms to give heterotrileptic [Na{N(SiMe₃)Dipp}(HMDS)Fe(C₆F₅)]_∞ ( 4 ). Attempts to deprotonate less activated pyridine led to the isolation of NaHMDS and heteroleptic Fe(II) amide [(py)Fe{N(SiMe₃)Dipp}(HMDS)] ( 5 ), resulting from an alternative redistribution process which is favoured by the Lewis donor ability of this substrate.     

Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering

Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)₃²⁺ for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts.

Artificial metalloenzyme visible light photocatalysts possess enhanced optical properties and are competent towards single electron and energy transfer organic transformations.     

Synthesis of mesocyclic and macrocyclic polythioethers using the cesium dithiolate technique

The mesocyclic trithioethers, 1,4,7-trithiacyclodecane, 1,4,7-trithiacycloundecane, 1,4,8-trithiacycloundecane, and 1,5,9-trithiacyclododecane; the mesocyclic trithioether ketones, 1,4,7-trithiacyclodecan-9-one; 1,4,8-trithiacycloundecan-6-one, and 1,5,9-trithiacyclododecan-3-one; and the mesocyclic trithioether alcohols, 1,4,7-trithiacyclodecan-9-ol, 1,4,8-trithiacycloundecan-6-ol, and 1,5,9-trithiacyclododecan-3-ol, have been synthesized using the cesium dithiolate technique. In some cases, the corresponding macrocyclic hexathioether was isolated from the reaction mixture in addition to the mesocyclic trithioether; 1,4,7,11,14,17-hexathiacycloeicosane, 1,4,7,11,14,17-hexathiacycloeicosan-9,19-dione, 1,4,7,12,15,18-hexathiacyclodocosane, and 1,5,9,13,17,21-hexathiacyclotetracosane. Single-crystal X-ray structures have been determined for 1,5,9-trithiacyclododecan-3-ol and 1,4,7,12,15,18-hexathiacyclodocosane. For 1,5,9-trithiacyclododecane-3-ol, the compound crystallizes in the monoclinic space group, C2/c, with a = 10.5926( 9 ) Å, b = 15.582(2) Å, c = 13.6015(8) Å, β = 98.186(6)⁰, Z = 8, and R = 0.038. The macrocycle, 1,4,7,12,15,18-hexathiacyclodocosane, crystallizes in the orthorhombic space group, Pbca, with a = 21.406(5) Å, b = 9.810(2) Å, c = 10.225(2) Å, Z = 4, and R = 0.020.     

Gas hydrate single-crystal structure analyses

The first single-crystal diffraction studies on methane, propane, methane/propane, and adamantane gas hydrates SI, SII, and SH have been performed. To circumvent the problem of very slow crystal growth, a novel technique of in situ cocrystallization of gases and liquids resulting in oligocrystalline material in a capillary has been developed. With special data treatment, termed oligo diffractometry, structural data of the gas hydrates of methane, acetylene, propane, a propane/ethanol/methane-mixture and an adamantane/methane-mixture were obtained. Cell parameters are in accord with reported values. Host network and guest are subject to extensive disorder, reducing the reliability of structural information. It was found that most cages are fully occupied by a guest molecule with the exception of the dodecahedral cage in the acetylene hydrate which is only filled to 60%. For adamantane in the icosahedral cage a disordered model is proposed.