Conformational behaviour and inclusion compound forming properties of 5,18-disubstituted derivatives of 5, 11, 12, 18-tetrahydrotribenzo[b,f,j][1,4]diazacyclododecine-6, 17-dione

An X-ray structure analysis shows that the 5, 18-dimethyl derivative ($\text{5}$) of the title compound ($\text{4}$) crystallises from xylene as a 1:1 inclusion compound in which the host molecules adopt propeller-like conformations ($\text{7}$ and $\text{7}$*) with almost perfect $\text{C}$₂ symmetry. Dynamic ¹H n.m.r. spectroscopy shows that the 5, 18-dibenzyl derivative ($\text{6}$) of ($\text{4}$) forms a 1:1 inclusion compound with ethanol in the solid state and undergoes ring inversion ($\text{7}$ ? $\text{7}$*) between enantiomeric propeller-like conformations in solution against a barrier of 21.1 kcal mol^?1     

Three‐Dimensional Architectures Incorporating Stereoregular Donor–Acceptor Stacks

We report the synthesis of two [2]catenane‐containing struts that are composed of a tetracationic cyclophane (TC⁴⁺) encircling a 1,5‐dioxynaphthalene (DNP)‐based crown ether, which bears two terphenylene arms. The TC⁴⁺ rings comprise either 1) two bipyridinium (BIPY²⁺) units or 2) a BIPY²⁺ and a diazapyrenium (DAP²⁺) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO₃)₂?2.5 H₂O to yield Cu‐paddlewheel‐based MOF‐1050 and MOF‐1051. The solid‐state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid‐like 2D networks. These 2D sheets are then held together by infinite donor–acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers—namely, the enantiomeric RR and SS forms—are observed in the crystals. An additional element of co‐conformational selectivity is present in MOF‐1051 as a consequence of the substitution of one of the BIPY²⁺ units by a DAP²⁺ unit: only the translational isomer in which the DAP²⁺ unit is encircled by the crown ether is observed. The overall topologies of MOF‐1050 and MOF‐1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures.     

Towards mechanically-linked polymers

This short review describes the progress which is being made towards the self-assembly of mechanically-linked polymers. A new concept in polymer synthesis - self-assembly - is demonstrated to have the potential to create novel high molecular weight polymers which possess repeat units that do not just consist of a main chain backbone built up of entirely covalent bonds, but are constructed of mechanical linkages comprised of catenane and rotaxane motifs.     

Computer-generated, three-dimensional reconstruction of histological parallel serial sections displaying microvascular and glandular structures in human endometrium

This paper describes a technique to develop high-resolution three-dimensional (3D) images of microvasculature structures in curettage, hysterectomy or endometrial resection biopsies using parallel histological serial sections. Employing a labelled streptavidin-biotin-alkaline phosphatase (LSAB(+)) method and visualising by using DAB(+) with the primary antibody, mouse anti human Q-Bend-10, the images were directly digitised from a light microscope into the KS400 Universal Image Processing and Analysis software via a CCD colour camera; binary images of the structures were created and the binary images were exported into VoxBlast 3D rendering software to view still and rotating 3D images on a computer monitor. This in turn enabled hard copies of the full sequence to be printed.     

First and second moments for self‐similar couplings and Wasserstein distances

We study aspects of the Wasserstein distance in the context of self‐similar measures. Computing this distance between two measures involves minimising certain moment integrals over the space of couplings, which are measures on the product space with the original measures as prescribed marginals. We focus our attention on self‐similar measures associated to equicontractive iterated function systems consisting of two maps on the unit interval and satisfying the open set condition. We are particularly interested in understanding the restricted family of self‐similar couplings and our main achievement is the explicit computation of the 1st and 2nd moment integrals for such couplings. We show that this family is enough to yield an explicit formula for the 1st Wasserstein distance and provide non‐trivial upper and lower bounds for the 2nd Wasserstein distance for these self‐similar measures.     

The Story of the Little Blue Box: A Tribute to Siegfried Hünig

The tetracationic cyclophane, cyclobis(paraquat-p-phenylene), also known as the little blue box, constitutes a modular receptor that has facilitated the discovery of many host–guest complexes and mechanically interlocked molecules during the past 35 years. Its versatility in binding small π-donors in its tetracationic state, as well as forming trisradical tricationic complexes with viologen radical cations in its doubly reduced bisradical dicationic state, renders it valuable for the construction of various stimuli-responsive materials. Since the first reports in 1988, the little blue box has been featured in over 500 publications in the literature. All this research activity would not have been possible without the seminal contributions carried out by Siegfried Hünig, who not only pioneered the syntheses of viologen-containing cyclophanes, but also revealed their rich redox chemistry in addition to their ability to undergo intramolecular π-dimerization. This Review describes how his pioneering research led to the design and synthesis of the little blue box, and how this redox-active host evolved into the key component of molecular shuttles, switches, and machines.     

Efficient templated synthesis of donor-acceptor rotaxanes using click chemistry

The mild reaction conditions, remarkable functional group compatibility, and complete regioselectivity of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition ("click chemistry") between organic azides and terminal alkynes have led to a threading-followed-by-stoppering approach to the synthesis of donor-acceptor rotaxanes incorporating cyclobis(paraquat-p-phenylene) (CBPQT4+) as the pi-accepting ring component. Rotaxane formation is initiated by reacting azide-functionalized pseudorotaxanes containing pi-donating 1,5-dioxynaphthalene (DNP) recognition units with appropriate alkyne-functionalized stoppers. The high yields obtained in this efficient, kinetically controlled post-assembly covalent modification, as well as the excellent convergence of the synthetic protocol, are demonstrated by the preparation of [2]-, [3]-, and [4]rotaxanes containing multiple DNP/CBPQT4+ donor-acceptor recognition motifs.     

Oxonitriles: a grignard addition-acylation route to enamides

[reaction: see text] Sequential addition of three different Grignard reagents and pivaloyl chloride to 3-oxo-1-cyclohexene-1-carbonitrile installs four new bonds to generate a diverse array of cyclic enamides. Remarkably, formation of the C-magnesiated nitrile intermediate is followed by preferential acylation by pivaloyl chloride rather than consumption by an in situ Grignard reagent. Rapid N-acylation of the C-magnesiated nitrile generates an acyl ketenimine that reacts readily with Grignard reagents or a trialkylzincate, effectively assembling highly substituted, cyclic enamides.