Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Cryptophanes with flexible linkers derived from (±)-tris-(4-formyl-phenyl)-cyclotriguaiacylene with either bisoxydi(ethylamine) or bis(aminopropyl)ether were isolated as single crystals, the crystal structures of which showed the proposed, but previously uncharacterised, out-in conformation, in which both cyclotriguaiacylene fragments adopt a crown conformation with one crown sitting inside the other. The usual cage-like out-out conformation of the cryptophanes was observed when crystals were dissolved upon heating, and the molecules collapsed back to the out-in isomers over time. In contrast, a cryptophane also derived from (±)-tris-(4-formyl-phenyl)-cyclotriguaiacylene but with rigid dibenzalhydrazine linkers was isolated as the more usual out-out isomer.     

Tris-N-alkylpyridinium-functionalised cyclotriguaiacylene hosts as axles in branched [4]pseudorotaxane formation

A series of [4]pseudorotaxanes composed of three-way axle threads based on the cyclotriguaiacylene family of crown-shaped cavitands and three threaded macrocyclic components has been achieved. These exploit the strong affinity for electron-poor alkyl-pyridinium units to reside within the electron-rich cavity of macrocycles, in this case dimethoxypillar[5]arene (DMP). The branched [4]pseudorotaxane assemblies {(DMP)₃?L}³⁺,where L = N-alkylated derivatives of the host molecule (±)-tris-(isonicotinoyl)cyclotriguaiacylene, were characterised by NMR spectroscopy and mass spectrometry, and an energy-minimised structure of {(DMP)₃?(tris-(N-propyl-isonicotinoyl)cyclotriguaiacylene)}³⁺ was calculated. Crystal structures of N-ethyl-isonicotinoyl)cyclotriguaiacylene hexafluorophosphate and N-propyl-isonicotinoyl)cyclotriguaiacylene hexafluorophosphate each show ‘hand-shake’ self-inclusion motifs occurring between the individual cavitands.     

Spectral transitions from the Rydberg autoionization states of a Li-like Mg X ion

Satellite lines caused by radiative transitions from the Rydberg autoionization states of a Li-like Mg X ion in a plasma heated by radiation from a XeCl and a Nd laser are identified for the first time, and their wavelengths are measured precisely. Comparison of the experimental data with the atomic structures calculated by the method of relativistic perturbation theory shows that the accuracy of calculations of the energy of autoionization states is rather high even without the use of any semiempirical corrections and is of the order of 0.06%. The experimentally measured wavelengths can be used for a semiempirical estimate of the value of the leading order of perturbation theory among the orders that were neglected in calculations. It is shown that the simulation of the population kinetics of Rydberg autoionization states of Li-like ions in a dense plasma should take into account all possible channels of dielectronic capture, in particular, from the excited states of a He-like ion. The precision experimental wavelengths obtained for satellites of the He_ß and He_γ lines of the Mg XI ion make possible to use these satellites as reference lines in studies of complicated spectra of multielectron ions.     

High‐throughput droplet‐based microfluidics for directed evolution of enzymes

Natural enzymes have evolved over millions of years to allow for their effective operation within specific environments. However, it is significant to note that despite their wide structural and chemical diversity, relatively few natural enzymes have been successfully applied to industrial processes. To address this limitation, directed evolution (DE) (a method that mimics the process of natural selection to evolve proteins toward a user‐defined goal) coupled with droplet‐based microfluidics allows the detailed analysis of millions of enzyme variants on ultra‐short timescales, and thus the design of novel enzymes with bespoke properties. In this review, we aim at presenting the development of DE over the last years and highlighting the most important advancements in droplet‐based microfluidics, made in this context towards the high‐throughput demands of enzyme optimization. Specifically, an overview of the range of microfluidic unit operations available for the construction of DE platforms is provided, focusing on their suitability and benefits for cell‐based assays, as in the case of directed evolution experimentations.     

Multimodal radio- (PET/SPECT) and fluorescence imaging agents based on metallo-radioisotopes: current applications and prospects for development of new agents

This perspective focuses on complexes of radioactive metal ions applied in multimodal radio- and optical imaging. The application of metal ions in radioimaging techniques such as Positron Emission Tomography (PET) and Single Photon Emission Computed Tomography (SPECT) has advantages over lighter nuclei in terms of half-life, but there are particular issues related to their speciation (particularly leaching from complexes) and with the combination of certain ions with fluorescent systems. The basic coordination chemistry of the ions involved and issues relating to biological conditions and their compatibility with optical imaging techniques are reviewed, the current literature presented in context, and the prospect of exploiting the intrinsic luminescence of certain metal-ligand complexes is discussed.     

Complexes in context: attempting to control the cellular uptake and localisation of rhenium fac-tricarbonyl polypyridyl complexes

Transition metal lumophores are now well established as agents for cell imaging, but we are still not able to predict generally and with confidence their cellular localisation, or, for that matter, their uptake efficiencies. While many such complexes have been shown to illuminate cells, genuine applications in biomedical research will only be developed when their uptake and localisation are better understood. This perspective is not a comprehensive review of luminescence, but is an overview of attempts to control uptake and localisation, focussing on a personal account of this group's development of imaging agents based on the Re(CO)(3) bipyridine core, and our attempts to understand and control their cellular behaviour.     

Hydrogenation of

The course of the hydrogenation of [5]- and [6]metacyclophane (1b and 1c) and their thermochemistry is described. Both compounds are hydrogenated rapidly (within 10 s) to furnish the bridgehead olefins 13b and 12c. The accompanying hydrogenation enthalpies are -220 and -141 kJmol(-1), respectively. Strain energies (SE) and olefinic strains (OS) of a number of bridgehead olefins have been evaluated by DFT calculations; it was concluded that 13b belongs to the class of hyperstable olefins which correlates nicely with its reluctance to undergo hydrogenation. By combining experimental hydrogenation enthalpies and DFT calculations, SE of 187 and 121 kJmol(-1) were derived for 1b and 1c.     

二苯并噻吩在分散型钼催化剂和原位产生的氢存在下的加氢脱硫Ⅳ. 集总动力学(英)

研究了水／ 甲苯乳化液中二苯并噻吩（ 硫芴） 在分散型钼酸、磷钼酸和四硫代钼酸铵催化剂存在下的加氢脱硫反应． 反应在高压釜中于３４０ ℃及三种不同的气氛即Ｈ２ , Ｈ２／Ｈ２Ｏ 和ＣＯ／Ｈ２Ｏ（ＣＯ 和Ｈ２Ｏ 经水煤气转换反应（ ＷＧＳＲ） 产生原位氢） 的存在下进行． 用ＧＣ 和ＧＣＭＳ鉴定、分析了气体和液体产物的组成． 在此基础上,提出了包含直接氢解和加氢脱硫两个反应途径的硫芴加氢反应网络,并采用最优化法计算了反应网络的速率常数． 结果表明： 对所研究的９ 个反应体系,反应网络的模型预测值与试验值十分吻合; 加氢路径比氢解路径至少快１ 倍,硫芴的加氢比联苯的加氢快１ 倍,部分加氢的中间产物１ ,２ ,３ ,４四氢硫芴和１ ,２ ,３ ,４ ,１０,１１六氢硫芴的氢解比硫芴直接氢解快１０ 倍以上; 对硫芴的加氢脱硫反应,在分散型钼存在下,原位产生的氢比加入的氢气更为有效．     

Effect of supercritical CO2 on bulk hydrogenation of nitrile butadiene rubber catalyzed by RhCl(PPh3)3

The effect of supercritical (SC) CO₂ on the bulk hydrogenation of NBR entrapped with the catalyst (RhCl(PPh₃)₃) was investigated under various reaction times, reaction temperatures, hydrogen pressures and loadings of the catalyst and the thicknesses of the polymer films. CO₂ helps in improving the transport behaviour of catalyst in polymer matrices, as well as helping to move catalyst into or out of the polymer. A method for the measurement of the dissolution extent or the apparent solubility of the Rh based catalyst in SC-CO₂ was developed. It is found that high temperatures and high SC-CO₂ densities would enhance the apparent solubility. Cosolvents, such as acetone, are also found to increase the apparent solubility. Details on the hydrogenation process are also presented.