Naphthylbipyrrole-Containing Amethyrin Analogue: A New Ligand for the Uranyl (UO) Cation.

Using naphthobipyrrole as a functional building block, a new expanded porphyrin, naphthoisoamethyrin, was prepared in 85% yield under acid-catalyzed [4 + 2] MacDonald coupling conditions. Treatment of naphthoisoamethyrin with the nonaqueous uranyl silylamide salt [UO[N(SiMe)]·2THF] yielded the corresponding uranyl complex. Upon metalation, naphthoisoamethyrin undergoes a two-electron oxidation to yield a formal 22 π-electron aromatic species, as inferred from H NMR and UV-vis spectroscopy, as well as cyclic voltammetry.

Flexible imidazolium macrocycles: building blocks for anion-induced self-assembly.

This feature article summarises recent contributions of the authors in the area of anion-induced supramolecular self-assembly. It is based on the chemistry of a set of tetracationic imidazolium macrocycles, specifically the so-called 'Texas-sized' molecular box, cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene) (1), and its congeners, cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,2-dimethylenebenzene) (2), cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,3-dimethylenebenzene) (3), and cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](2,6-dimethylenepyridine) (4). These systems collectively have been demonstrated as being versatile building blocks that interact with organic carboxylate or sulfonate anions, as well as substrates (e.

Using anion recognition to control the folding and unfolding of a single chain phosphorescent polymer.

We report here the use of anion recognition to control the folding and unfolding of a single polymeric chain consisting of a PMMA bearing pendant calix[4]pyrrole and Pt(ii) porphyrin subunits.

Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion-Pair Receptor.

Current approaches to lowering the pH of basic media rely on the addition of a proton source. An alternative approach is described herein that involves the liquid-liquid extraction-based removal of cesium salts, specifically CsOH and Cs CO , from highly basic media. A multitopic ion-pair receptor (2) is used that can recognize and extract the hydroxide and carbonate anions as their cesium salts, as confirmed by H NMR spectroscopic titrations, ICP-MS, single-crystal structural analyses, and theoretical calculations.

A synthetic ion transporter that disrupts autophagy and induces apoptosis by perturbing cellular chloride concentrations.

Perturbations in cellular chloride concentrations can affect cellular pH and autophagy and lead to the onset of apoptosis. With this in mind, synthetic ion transporters have been used to disturb cellular ion homeostasis and thereby induce cell death; however, it is not clear whether synthetic ion transporters can also be used to disrupt autophagy. Here, we show that squaramide-based ion transporters enhance the transport of chloride anions in liposomal models and promote sodium chloride influx into the cytosol.

A Mitochondria-Targeted Cryptocyanine-Based Photothermogenic Photosensitizer.

Cryptocyanine-based probes exhibit highly efficient photothermal conversion and represent a new class of photothermal agents for use in photothermal therapy (PTT). With the thermal susceptibility of mitochondria in mind, we have prepared a mitochondria-targeted, NIR-absorbing cryptocyanine probe (Mito-CCy) and evaluated its photophysical properties, photothermal conversion efficiency, biological compatibility, cytotoxicity, and mitochondrial localization in HeLa cells. Upon subjecting 0.

Molecular Recognition Under Interfacial Conditions: Calix[4]pyrrole-Based Cross-linkable Micelles for Ion Pair Extraction.

An anthracene-functionalized, long-tailed calix[4]pyrrole 1, containing both an anion-recognition site and cation-recognition functionality, has been synthesized and fully characterized. Upon ion pair complexation with FeF, receptor 1 self-assembles into multimicelles in aqueous media. This aggregation process is ascribed to a change in polarity from nonpolar to amphiphilic induced upon concurrent anion and cation complexation and permits molecular recognition-based control over chemical morphology under interfacial conditions.

A Bis-calix[4]pyrrole Enzyme Mimic That Constrains Two Oxoanions in Close Proximity.

Herein we describe a large capsule-like bis-calix[4]pyrrole 1, which is able to host concurrently two dihydrogen phosphate anions within a relatively large internal cavity. Evidence for the concurrent, dual recognition of the encapsulated anions came from H NMR and UV-vis spectroscopies and ITC titrations carried out in CDCl/CDOD (9/1, v/v) or dichloroethane (DCE), as well as single crystal X-ray diffraction analyses. Receptor 1 was also found to bind two dianionic sulfate anions bridged by two water molecules in the solid state.

Overcoming the Limits of Hypoxia in Photodynamic Therapy: A Carbonic Anhydrase IX-Targeted Approach.

A major challenge in photodynamic cancer therapy (PDT) is avoiding PDT-induced hypoxia, which can lead to cancer recurrence and progression through activation of various angiogenic factors and significantly reduce treatment outcomes. Reported here is an acetazolamide (AZ)-conjugated BODIPY photosensitizer (AZ-BPS) designed to mitigate the effects of PDT-based hypoxia by combining the benefits of anti-angiogenesis therapy with PDT. AZ-BPS showed specific affinity to aggressive cancer cells (MDA-MB-231 cells) that overexpress carbonic anhydrase IX (CAIX).

Synthesis and characterization of a dipyriamethyrin-uranyl complex.

The reaction between non-aqueous uranyl silylamide (UO[N(SiMe)]·2THF) under anaerobic conditions or uranyl acetate (UO(OAc)·2HO) under standard laboratory conditions and dipyriamethryin affords a bench-stable uranyl complex. Competition studies as well as DFT calculations provide support for the observed selectivity for the uranyl cation over trivalent lanthanide and multiple transition metal precursors.

Expanded Rosarin: A Versatile Fullerene (C) Receptor.

An expanded rosarian (PP) with a bowl-like conformation has been prepared and characterized in a one-pot procedure that involves condensing a bispyrrole pyridine precursor (PP) with benzaldehyde, followed by oxidation. Single crystal X-ray diffraction analysis reveals a bowl-like conformation in the solid state with an upper rim diameter defined by the meso-phenyl substituents of ca. 13.

Structural, Photophysical, and Magnetic Circular Dichroism Studies of Three Rigidified meso-Pentafluorophenyl-Substituted Hexaphyrin Analogues.

Detailed electronic, structural, photophysical, and redox studies of a series of meso-pentafluorophenyl-substituted hexaphyrins, namely amethyrin (1), rosarin (2), and rubyrin (3), are described. In prior work, it was found that the electronic states of the antiaromatic hexapyrrolic macrocycle, [24]rosarin 2, could be modified by exposure to several Brønsted acids (e.g.

Discrete 1 : 1 complexes and higher order assemblies formed from aminobenzene sulphonate anions and a tetraimidazolium "molecular box".

Use of isomeric aminobenzene sulphonate anions in conjunction with a tetraimidazolium "molecular box" leads to self-assembled embedded structures. Simple 1 : 1 complexes are formed at low concentrations in DMSO when the host : guest ratio is 1.0.

Liposomal Texaphyrin Theranostics for Metastatic Liver Cancer.

Reported here is a new theranostic agent, 1, which consists of a Gd-texaphyrin core conjugated to a doxorubicin prodrug via a disulfide bond. Conjugate 1 was designed to undergo cleavage in the presence of glutathione (GSH), a species typically upregulated in cancer cells. As prepared, conjugate 1 displays no appreciable fluorescence.

Tetrathiafulvalene- (TTF-) Derived Oligopyrrolic Macrocycles.

After the epochal discovery of the "organic metal", namely, tetrathiafulvalene (TTF)-7,7,8,8-tetracyano-p-quinodimethane (TCNQ) dyad in 1973, scientists have made efforts to derivatize TTF for constructing various supramolecular architectures to control the charge-transfer processes by adjusting the donor-acceptor strength of the dyads for numerous applications. The interesting inherent electronic donor properties of TTFs control the overall electrochemical properties of the supramolecular structures, leading to the construction of highly efficient optoelectronic materials, photovoltaic solar cells, organic field-effect transistors, and optical sensors. Modified TTF structures thus constitute promising candidates for the development of so-called "functional materials" that could see use in modern technological applications.

Controlling amphiphilic copolymer self-assembly morphologies based on macrocycle/anion recognition and nucleotide-induced payload release.

We report here a new approach to creating diversiform copolymer-derived self-assembly morphologies that relies on macrocycle/anion recognition in aqueous media. This approach exploits the anion binding features of a water-soluble form of the so-called 'Texas-sized' molecular box. When this tetracationic receptor is added to an aqueous solution of an amphiphilic copolymer bearing tethered carboxylate anion substituents, binding occurs to form a macrocycle/polymer complex.

Unprecedented Double aza-Michael Addition within a Sapphyrin Core.

A novel sapphyrin derivative was obtained from the reaction between a free-base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza-Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units.

3-(Dicyanomethylidene)indan-1-one-Functionalized Calix[4]arene-Calix[4]pyrrole Hybrid: An Ion-Pair Sensor for Cesium Salts.

A chromogenic calix[4]arene-calix[4]pyrrole hybrid ion pair receptor bearing an indane substituent at a β-pyrrolic position has been prepared. On the basis of solution-phase UV-vis spectroscopic analysis and (1)H NMR spectroscopic studies carried out in 10% methanol in chloroform, receptor 1 is able to bind only cesium ion pairs (e.g.

Acid-triggered release of doxorubicin from a hydrazone-linked Gd(3+)-texaphyrin conjugate.

The hydrazone-based Gd(3+)-texaphyrin doxorubicin conjugate 1, releases active doxorubicin at acidic pH values, allowing its components to be followed by two complementary imaging methods, namely Off-On fluorescence enhancement and MR imaging. It thus acts as a promising theranostic agent.

Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium Nitrite.

The hemispherand-strapped calix[4]pyrrole (1) acts as an ion pair receptor that exhibits selectivity for lithium salts. In organic media (CD2Cl2 and CD3OD, v/v, 9:1), receptor 1 binds LiCl with high preference relative to NaCl, KCl, and RbCl. DFT calculations provided support for the observed selectivity.

Activation of Platinum(IV) Prodrugs By Motexafin Gadolinium as a Redox Mediator.

Water-soluble platinum(IV) prodrugs, which proved kinetically stable to reduction in the presence of physiological concentration of ascorbate, were quickly reduced to their active form, oxaliplatin, when co-incubated with a macrocycle metallotexaphyrin (i.e., Motexafin Gadolinium (MGd)).

Programmed activation of cancer cell apoptosis: A tumor-targeted phototherapeutic topoisomerase I inhibitor.

We report here a tumor-targeting masked phototherapeutic agent 1 (PT-1). This system contains SN-38-a prodrug of the topoisomerase I inhibitor irinotecan. Topoisomerase I is a vital enzyme that controls DNA topology during replication, transcription, and recombination.

Post-synthetic modification of a macrocyclic receptor regioselective imidazolium ring-opening.

A facile post-synthetic modification of a tetracationic tetraimidazolium macrocycle, (, the "Texas-sized" molecular box (cyclo[2](2,6-di(1-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene)), is described. Under mild basic conditions, ring-opening of the imidazolium moieties occurs. This results in two new isomeric dicationic macrocycles.

Ship in a breakable bottle: fluoride-induced release of an organic molecule from a Pr(iii)-linked molecular cage.

A 3-dimensional networked molecular cage, , has been synthesized. This macrocycle-based framework was prepared from a solvothermal reaction involving a flexible organic building block, calix[4]pyrrole dibenzoic acid (H2), and Pr(NO3)3·6H2O. A unique feature of is that it retains free calix[4]pyrrole molecules in the framework pores.