No abstract

Biofoundries provide an integrated infrastructure to enable the rapid design, construction, and testing of genetically reprogrammed organisms for biotechnology applications and research. Many biofoundries are being built and a Global Biofoundry Alliance has recently been established to coordinate activities worldwide.

1. General Methods All reagents were purchased from commercial suppliers (Aldrich or Fisher) and used without further purification. Cyclobis(paraquat-4,4′-biphenylene) tetrakis(hexafluorophosphate) S1 (1•4PF6), 4,4′(5′)-bis[2-(2-{2-(propargyl)ethoxy}ethoxy)ethoxy]tetrathiafulvalene S2 (7), the TTF/ DNP macrocycle S3 4, and 1,1ʹ′-[4,4ʹ′-biphenylenebis-(methylene)]bis(4,4ʹ′-bipyridinium) bis (hexafluorophosphate) S4 (5•2PF6) were prepared according to literature procedures. Thin layer chromatography (TLC) was performed on silica gel 60 F254 (E. Merck). Column chromatography was performed on silica gel 60F (Merck 9385, 0.040-0.063 nm). Nuclear magnetic resonance (NMR) spectra were recorded at 25 ˚C (unless otherwise noted) on Bruker Avance 500 and 600 spectrometers, with working frequencies of 500 and 600 MHz for 1 H, and 125 and 150 MHz for 13 C nuclei, respectively. Chemical shifts are reported in ppm relative to the signals corresponding to the residual non-deuterated solvents S5. All 13 C spectra were recorded with the simultaneous decoupling of proton nuclei. UV-Vis-NIR absorbance spectra

A new class of mechanized silica nanoparticles, which exploits the stability of the inclusion complexes formed between ferrocenedicarboxylic acid and both cucurbit [7]uril (CB7) and β-cyclodextrin (β-CD), are described. Mesoporous silica nanoparticles, capable of storing a payload of small molecules and releasing it following particular activation processes, have been designed and decorated with ferrocenecarboxylic acid stalks. The storage and release of the payload is controlled by the host-guest interaction between the ferrocene moiety (guest) and the ring moiety (CB7 or β-

catenanes-composed of a tetracationic molecular square, cyclobis(paraquat-4,4 0 -biphenylene), as the π-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the π-electron rich components-have been investigated in order to study their ability to form TTF radical dimers. It has been proven that the mechanically interlocked nature of the [3]catenanes facilitates the formation of the TTF radical dimers under redox control, allowing an investigation to be performed on these intermolecular interactions in a so-called "molecular flask" under ambient conditions in considerable detail. In addition, it has also been shown that the stability of the TTF radical-cation dimers can be tuned by varying the secondary binding motifs in the [3]catenanes. By replacing the DNP station with a butadiyne group, the distribution of the TTF radical-cation dimer can be changed from 60% to 100%. These findings have been established by several techniques including cyclic voltammetry, spectroelectrochemistry and UV-vis-NIR and EPR spectroscopies, as well as with X-ray diffraction analysis which has provided a range of solid-state crystal structures. The experimental data are also supported by high-level DFT calculations. The results contribute significantly to our fundamental understanding of the interactions within the TTF radical dimers.