Corrin-based chemosensors allow the rapid and selective colorimetric detection of endogenous biological cyanide. The color change from orange to violet can be easily observed with the "naked eye" (Deltalambda(max) = 51 nm). The methodology works directly in the biological matrix without time-consuming sample pretreatment and the use of special reaction conditions. It was possible to study the enzymatic release of cyanide from its biological precursor linamarin with diffuse reflectance UV-visible (DRUV-vis) spectroscopy on a freshly prepared biological surface. These experiments were accompanied by stopped-flow kinetic measurements under homogeneous conditions. Detection in the biological sample is based on the selective coordination of cyanide to the metal-based chemosensor as proven by UV-vis and (1)H NMR spectroscopy. Examples of applications during food manufacturing are given.

Substitution of Co(III)-bound water by cyanide allows the rapid colorimetric detection of micromolar amounts of cyanide with cobalt corrinoids. Negatively charged side chains at the periphery of these metal-based sensors increase the selectivity of cyanide versus thiocyanate, the most disturbing anion, by a factor of 30 through additional supramolecular interactions in water.

"Base on"/"base off" coordination of the intramolecular bound benzimidazole nucleobase of vitamin B 12 allows the specific colorimetric detection of millimolar concentrations of cyanide in water. In various competition experiments, it was demonstrated that up to 12 different anions as well as a 1000-fold excess of Cl (-) over CN (-) do no interfere with the sensor. An 8-fold increased sensitivity in the "naked eye" detection of CN (-) was observed when water was replaced by MeOH/H 2O (5%) as a solvent.

This Feature Article highlights recent developments in the field of vitamin B12 derivatives for medicinal applications. The following topics are emphasized: (1) the development of aquacorrinoids for cyanide detection and detoxification, (2) the use of vitamin B12 conjugates and (3) antivitamins B12 for therapy and diagnosis, and (4) the design of corrinoids as activators of soluble guanylyl cyclase (sGC).

Antivitamins represent a broad class of compounds that counteract the essential effects of vitamins. The symptoms triggered by such antinutritional factors resemble those of vitamin deficiencies, but can be successfully reversed by treating patients with the intact vitamin. Despite being undesirable for healthy organisms, the toxicities of these compounds present considerable interest for biological and medicinal purposes. Indeed, antivitamins played fundamental roles in the development of pioneering antibiotic and antiproliferative drugs, such as prontosil and aminopterin. Their development and optimisation were made possible by the study, throughout the 20th century, of the vitamins' and antivitamins' functions in metabolic processes. However, even with this thorough knowledge, commercialised antivitamin-based drugs are still nowadays limited to antagonists of vitamins B9 and K. The antivitamin field thus still needs to be explored more intensely, in view of the outstanding therapeutic success exhibited by several antivitamin-based medicines. Here we summarise historical achievements and discuss critically recent developments, opportunities and potential limitations of the antivitamin approach, with a special focus on antivitamins K, B9 and B12 .

This communication describes a disassembly based approach for the detection of biologically relevant di- and triphosphates in water using locked fluorescent salicylaldehyde probes.

Inorganic pyrophosphate( PPi)i sc onsidereda sa diagnostic marker for various diseasess uch as cancer and vascular calcification. PPi also plays an important preservative role as an additiveE 450 in foodstuff. In this work, as elective Fe III -salen-basedp robe for PPi is described;t his probe disassembles in the presence of the target analyte into its molecular blocks, 1,2-propanediamine and 3-chloro-5-formyl-4-hydroxybenzenesulfonic acid. The latter signaling unit leads to afluorometric response. Compared with arelated prototype, the new complex shows a2 .3-times stronger emission at 500 nm and a1 55-times better selectivity of PPi over adenosine triphosphate( ATP). Importantly,t he new probew as successfully applied for detectingE 450 in foodstuff.

Inorganic pyrophosphate (PPi) is produced from nucleoside triphosphates in important biosynthetic reactions and is considered a diagnostic marker for various diseases, such as cancer, crystal deposition disease, and arthritis. Traditional methods for biological PPi detection rely on off-line analytics after sample destruction. Molecular probes for imaging this biologically important analyte with temporal and spatial control in living cells are currently in demand. Herein, we report an Fe(III) -salen complex as the first small reaction-based probe for endogenous mitochondrial PPi following a disassembly approach. Significantly, we successfully applied this complex for the detection of increased cellular PPi levels, and its performance was not affected by the presence of mitochondrial ATP in living cells.