Formalising the Pathways to Life Using Assembly Spaces

Assembly theory (referred to in prior works as pathway assembly) has been developed to explore the extrinsic information required to distinguish a given object from a random ensemble. In prior work, we explored the key concepts relating to deconstructing an object into its irreducible parts and then evaluating the minimum number of steps required to rebuild it, allowing for the reuse of constructed sub-objects. We have also explored the application of this approach to molecules, as molecular assembly, and how molecular assembly can be inferred experimentally and used for life detection. In this article, we formalise the core assembly concepts mathematically in terms of assembly spaces and related concepts and determine bounds on the assembly index. We explore examples of constructing assembly spaces for mathematical and physical objects and propose that objects with a high assembly index can be uniquely identified as those that must have been produced using directed biological or technological processes rather than purely random processes, thereby defining a new scale of aliveness. We think this approach is needed to help identify the new physical and chemical laws needed to understand what life is, by quantifying what life does.     

A compact UHV package for microfabricated ion-trap arrays with direct electronic air-side access

We have demonstrated a new apparatus for operating microfabricated ion-trap arrays in a compact ultra-high-vacuum setup with excellent optical and electrical access. The approach uses conventional components, materials and techniques in a unique fashion. The microtrap chip is mounted on a modified ceramic leadless chip carrier, the conductors of which serve as the vacuum feedthrough. The chip carrier is indium-sealed to stainless-steel components to form vacuum seals, resulting in short electrical path lengths of ≤20 mm from the trap electrodes under vacuum to air side. The feedthrough contains conductors for the radio-frequency trap drive, as well as 42 conductors for DC electrodes. Vacuum pressures of ～1 × 10^?11 mbar are achieved, and ions have been confined and laser cooled in a microtrap chip. The apparatus enables accurate measurements of radio-frequency voltage amplitudes on the trap electrodes, yielding an excellent agreement between measured and modelled trap efficiencies. This feature is of significant use in establishing initial operation of new devices. The principle of the connectivity scheme presented here is applicable to larger ceramic chip carriers containing many more conductors.     

Waveguide arrays as plasmonic metamaterials: transmission below cutoff

Since the work of Ebbesen et al. [Nature (London) 391, 667 (1998)], there has been immense interest in the optical properties of subwavelength holes in metal layers. While the enhanced transmission observed is generally associated with surface plasmon polaritons (SPPs), theoretical predictions suggest a similar response with perfectly conducting materials. However, Pendry et al. [Science 305, 847 (2004)] proposed that, if textured on a subwavelength scale, even perfect conductors support surface modes. Here, using microwave radiation incident upon an array of metal waveguides, we observe peaks in the transmissivity below cutoff and confirm the crucial role of these SPP-like modes in the mechanism responsible.     

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.     

Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron‐Rich Substrates

Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene‐types and tolerance of electron‐rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene‐types that is tolerant of electron‐rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex‐cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales.     

Dopant type dependency of domain development in rare-earth-doped ceria: An explanation by computer simulation of defect clusters

Defect clusters in several rare-earth-doped ceria (doped with Y, Sm, Gd, Dy and Yb) containing up to four oxygen vacancies and eight dopant cations have been simulated and compared. In all doped ceria systems, the binding energy of the clusters increases with increasing cluster size and the oxygen vacancies tend to form curved chains in the clusters. Moreover, the capability of the growth of defect cluster is affected by dopant type, which can explain the dopant type dependency of domain development with increasing doping concentration in heavily doped ceria.     

Highly efficient visible-light driven photochromism: developments towards a solid-state molecular switch operating through a triplet-sensitised pathway

We introduce a new highly efficient photochromic organometallic dithienylethene (DTE) complex, the first instance of a DTE core symmetrically modified by two Pt(II) chromophores [Pt(PEt(3))(2)(C≡C)(DTE)(C≡C)Pt(PEt(3))(2)Ph] (1), which undergoes ring-closure when activated by visible light in solvents of different polarity, in thin films and even in the solid state. Complex 1 has been synthesised and fully photophysically characterised by (resonance) Raman and transient absorption spectroscopy complemented by calculations. The ring-closing photoconversion in a single crystal of 1 has been followed by X-ray crystallography. This process occurs with the extremely high yield of 80%--considerably outperforming the other DTE derivatives. Remarkably, the photocyclisation of 1 occurs even under visible light (>400 nm), which is not absorbed by the non-metallated DTE core HC≡C(DTE)C≡CH (2) itself. This unusual behaviour and the high photocyclisation yields in solution are attributed to the presence of a heavy atom in 1 that enables a triplet-sensitised photocyclisation pathway, elucidated by transient absorption spectroscopy and DFT calculations. The results of resonance Raman investigation confirm the involvement of the alkynyl unit in the frontier orbitals of both closed and open forms of 1 in the photocyclisation process. The changes in the Raman spectra upon cyclisation have permitted the identification of Raman marker bands, which include the acetylide stretching vibration. Importantly, these bands occur in the spectral region unobstructed by other vibrations and can be used for non-destructive monitoring of photocyclisation/photoreversion processes and for optical readout in this type of efficiently photochromic thermally stable systems. This study indicates a strategy for generating efficient solid-state photoswitches in which modification of the Pt(II) units has the potential to tune absorption properties and hence operational wavelength across the visible range.