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Split nail (SN) is a rare type of nail fragility syndrome, characterized by a longitudinal fissure involving the entire thickness of the nail plate. Longitudinal nail splitting may be caused by direct injury to the nail plate or matrix insult. Few articles have been published on the topic, most were related to the traumatic aetiology. Some case reports mention tumours and inflammatory disorders as other causes.The aim of this retrospective study was to analyse the clinical and histopathological features of 56 SN collected at the nail consultation of the dermatology department at Saint Pierre University Hospital in Brussels, between 1997 and 2019.Fifty-six patients were included (34 women and 22 men) with median age of 44.2 years. The fingernails were 3.2 times more frequently affected than toenails, especially the thumb. The most frequent aetiologies were tumours (45.6%), inflammatory diseases (26.3%) and traumas (19.3%). Congenital (5.3%) and systemic disorders (3.5%) were rarer causes. Histopathological slide review confirmed that alteration of the nail matrix integrity causes split nail, resulting either from matrix stretching by an underlying tumour or from impairment of the keratinization process by inflammatory diseases, melanocytic tumours and Bowen's disease.This study is the largest case series of longitudinal nail splitting to date. It is the first to gather nail disorders causing SN with their clinical pathological correlation. The most common causes are traumatisms, tumours and inflammatory disorders. Congenital and systemic disorders are rarer. Tumours are responsible for half of the cases from which one third are malignant, mainly melanoma. When facing a monodactylic SN, benign as well as malignant tumours should be ruled out before concluding to traumatic aetiology.

In 1987, Pedersen, Cram, and Lehn were awarded the Nobel Prize in Chemistry to honor their achievements in, among other things, the selective recognition of alkali metal ions by synthetic hosts. Almost three decades later, the 2016 Nobel Prize went to Stoddart, Sauvage, and Feringa for the development of artificial molecular machines, in which interlocked molecules play a significant role. Surprisingly, although many rotaxane- and catenane-based molecular machines have been constructed using various templating approaches, alkali metal ions, which are good templates for crown ether synthesis, have only rarely been applied as templates for the assembly of these interlocked molecules. This paucity of examples is probably due to the less well defined coordination numbers and geometries in the complexation of alkali metal ions to common oxygen-containing ligands, resulting in much weaker metal-ligand interactions and less predictable structures for their complexes compared with those formed between transition metal ions and common pyridine-containing ligands. Nevertheless, the ease of removing alkali metal ions from interlocked compounds and their much lower toxicity compared with that of transition metal ions are attractive features that have inspired their use as templates in the synthesis of interlocked molecules. About a decade ago, we began investigating the feasibility of using alkali metal ions to template the formation of catenanes and rotaxanes, with the hope of developing facile, broadly applicable, green, and efficient methods for their construction. We noticed that the interactions between oxygen-containing ligands and alkali metal ions can be strengthened by minimizing the effects of competing interactions from solvent molecules and counteranions. Thus, to increase the solubility of the metal ion salts in less polar solvents (e.g., CH

Calixarenes are widely used as molecular platforms in supramolecular chemistry. Their efficient modification is key for appending functional moieties such as binding, sensing, chiral, or hydrophilic subunits. Due to the presence of multiple identical functional groups, selective functionalization of such macrocyclic compounds is highly challenging. Indeed, the control of the chemo-, regio-, stereo- as well as iteroselectivity is required. This review describes rational methods leading to a high degree of regio- and/or iteroselectivity and classifies them into specific strategies. Many of these strategies are conceptually very general and hopefully will be a source of inspiration for developing selective methods for other macrocyclic platforms.

[2]Rotaxanes displaying one-off photo-triggerable gelation properties have been synthesized through the "clipping" of photo-degradable macrocycles around the amide or urea functionalities of organo- and hydrogelators. Irradiation with UV-light cleaved the photo-labile macrocyclic components from the [2]rotaxanes, resulting in the free gelators being released into solution and, thereafter, forming gels. When the rate of gelation was sufficiently rapid, selective gelation of specific regions of the solution-and, indeed, photo-patterning of the solution-was possible.

Herpes simplex viruses are endemic worldwide, with an estimated seroprevalence of approximately 70% in developed countries. However, it is less well known that they are one of the viral causes of fulminant hepatitis (, info:eu-repo/semantics/published

The Huisgen thermal reaction between an organic azide and an acetylene was employed for the selective monofunctionalization of a X6 -azacryptand ligand bearing a tren coordinating unit [X6 stands for calix[6]arene and tren for tris(2-aminoethyl)amine]. Supramolecular assistance, originating from the formation of a host-guest inclusion complex between the reactants, greatly accelerates the reaction while self-inhibition affords a remarkable selectivity. The new ligand possesses a single amino-leg appended at the large rim of the calixarene core and the corresponding Zn(2+) complex was characterized both in solution and in the solid state. The coordination of Zn(2+) not only involves the tren cap but also the introverted amino-leg, which locks the metal ion in the cavity. Compared with the parent ligand deprived of the amino-leg, the affinity of the new monofunctionalized X6 tren ligand 6 for Zn(2+) is found to have a 10-fold increase in DMSO, which is a very competitive solvent, and with an enhancement of at least three orders of magnitude in CDCl3 /CD3 OD (1:1, v/v). In strong contrast with the fast binding kinetics, decoordination of Zn(2+) as well as transmetallation appeared to be very slow processes. The monofunctionalized X6 tren ligand 6 fully protects the metal ion from the external medium thanks to the combination of a cavity and a closed coordination sphere, leading to greater thermodynamic and kinetic stabilities.

Calixarenes are widely used as molecular platforms in supramolecular chemistry. Their efficient modification is key for appending functional moieties such as binding, sensing, chiral, or hydrophilic subunits. Due to the presence of multiple identical functional groups, selective functionalization of such macrocyclic compounds is highly challenging. Indeed, the control of the chemo-, regio-, stereo- as well as iteroselectivity is required. This review describes rational methods leading to a high degree of regio- and/or iteroselectivity and classifies them into specific strategies. Many of these strategies are conceptually very general and hopefully will be a source of inspiration for developing selective methods for other macrocyclic platforms.

Water is a unique solvent and the design of selective artificial hosts that can efficiently work in an aqueous medium is a challenging task. It is known that the calix[6]tren zinc complex can recognize neutral guests in organic solvents. This complex was incorporated into dodecylphosphocholine micelles (DPC) and studied by NMR. The incorporated complex is able to extract selectively primary amines from the aqueous environment driven by an important hydrophobic effect which also affects the selectivity of the complex for these amines. This work shows how the incorporation of organo-soluble receptors in micelles can be an elegant and very efficient strategy to obtain water compatible nanosized supramolecular recognition devices which can be prepared via a straightforward self-assembly process., info:eu-repo/semantics/published

The selective functionalization of macrocyclic receptors remains extremely challenging because it generally requires the transformation of one and only one functional group among several identical groups. Recently, some of us described that the host-guest properties of a calix[6]arene-based Zn complex could be exploited for its selective monofunctionalization. Herein, we report on the extension of this synthetic strategy to a calix[6]arene-based receptor displaying a different recognition pattern with its guest. More precisely, a calix[6]arene tris-carboxylic acid-based receptor bearing three azido groups at the large rim was selectively monofunctionalized through an intramolecular thermal Huisgen reaction with a hexynNH3(+) ion accommodated into the cavity. This work shows that the monofunctionalization methodology can also be performed efficiently with host-guest systems involving ionic/H-bonding interactions, and it is thus not limited only to the use of metal-ligand interactions. In other words, this supramolecular methodology can be used as a general tool for the selective functionalization of molecular receptors.