Porphyrins in troubled times: a spotlight on porphyrins and their metal complexes for explosives testing and CBRN defense

Abstract

A critical perspective on (metallo)porphyrins in security-related applications: the past, present and future of explosives detection, CBRN defense, and beyond.

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

“…[119] It should be highlighted that due to the wealth of literature on distorted porphyrins,a ny synoptic view can only be as creenshot of this fast-developing and diverse landscape,w ith their applications spanning from medicinal, optical, and technical uses to crystal engineering,m ethods development, [136] catalysis, [137] and sensing. [138] As we have shown, only the introduction of saddling results in significant NÀHe xposure and as such, this approach is the basis of anumber of new and up-and-coming methods for the binding and activation of small molecules. [132] C: Structures [58] of 47 (CCDC:TPHPOR10) [117a] and 84-87 (TATPOT01, TATPUZ01, TATQAG01, TATQEK01) in the crystal.…”

“…[4a,b,6d, 139, 142] Moreover,porphyrins are of interest for military and security-related applications and can counteract explosives (as in the case of 92-95)and hazardous biological, chemical, and radiological/nuclear materials ( Figure 25). [138,[143][144][145][146] However,c urrently this rarely involves the core of free-base porphyrins,l eaving plenty of room for new developments and to exploit the high potential of the NÀ H···X binding motif for probing.…”

Conformational Re‐engineering of Porphyrins as Receptors with Switchable N−H⋅⋅⋅X‐Type Binding Modes

“…[8] Therefore, the respective symmetric porphyrin dications have yet to find use as either functional or selective anion receptors under normal laboratory conditions. [9] Moreover,t he porphyrin inner core imine and amine units of planar analogues are usually not involved in intermolecular interactions due to the "shielding" properties of the macrocycle system. [10] Distortion can cause an increase in the degree of outwards orientation of the inner pyrrolic entities,making these positions more basic and accessible to substrates,t hereby creating an "active center".…”

Enhanced Cellular Uptake and Photodynamic Effect with Amphiphilic Fluorinated Porphyrins: The Role of Sulfoester Groups and the Nature of Reactive Oxygen Species

“…A major challenge in PDT is to develop PS molecules that absorb light in the phototherapeutic window-the 630-850 nm range-where human tissues are the most transparent. Porphyrin derivatives [5], including chlorins [6][7][8] and bacteriochlorins [6], as well as phthalocyanines [9][10][11], are the most frequently studied PDT photosensitizers due to their long-wavelength absorption and their photophysical properties (high yields of long-lived triplet states) [12][13][14][15]. The lowest-electronically excited triplet state of photosensitizer is the precursor of ROS-generating reactions.…”