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Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin-bisphenolate (DPP) complexes, we synthesized the gold(iii) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that the ground states of the new complexes indeed correspond to an innocent AuIII-DPP3-, paralleling a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand-centered oxidations, reduction of AuDPP is predicted to occur across both the metal and the ligand.

Four BODIPY dyes (6a-6d) with electron-donating or electron-withdrawing groups at the meso -position were synthesized by the Sonogashira coupling reaction of 2,5-diethynylthieno[3,2- b ]thiophene with mono-iodo-BODIPY moieties. All compounds were fully characterized by 1 H NMR and MALDI-TOF MS. Their photophysical and electrochemical properties were studied by UV-visible absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy, two-photon excitation spectroscopy and cyclic voltammetry. These conjugated dyes exhibit interesting photophysical properties such as a high molar extinction coefficient, large Stokes shift and high two-photon absorption cross section σ 2 .

The high risk of CO poisoning justifies the need for indoor air quality control and warning systems based on the detection of low concentrations (ppm-ppb) of CO. Cobalt corrole complexes selectively bind CO vs. O 2 , CO 2 , N 2 , opening new fields of applications. By combining the CO chemisorption properties of cobalt corroles with the known sorption capacity of MOFs, we hope to obtain high performance sensing materials for CO detection. In addition, the exposed metal sites of MOFs lead to CO 2 physisorption, allowing the co-detection of CO and CO 2 . In this work, PCN-222, a stable Zr-based MOF made from Ni(TCPP) with natural vacancies, has been used as a porous matrix for the grafting of electron-poor metallocorroles. The materials were characterized by powder XRD, SEM and optical microscopy, BET analyses and gas adsorption measurements at 298 K. No degradation of the crystalline structure of PCN-222 was observed. At 1 atm, the adsorbed CO (g) volumes measured for the best materials were 12.15 cm 3  g -1 and 14.01 cm 3  g -1 for CoCorr2@PCN-222 and CoCorr3@PCN-222 respectively, and both materials exhibited high CO chemisorption and selectivity against O 2 , N 2 , and CO 2 at low pressure due to the highest energy of the chemisorption process vs physisorption., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Herein, we have designed and synthesized two novel BODIPY dimer-based small molecules, denoted as ZMH-1 and ZMH-2, covalently linked and functionalized with triphenylamine (TPA) (ZMH-1) and carbazole (C Z ) (ZMH-2) units as the electron donor at the 3- and 5-positions of the BODIPY core, respectively. Their optical and electrochemical properties were investigated. We have fabricated all small molecule bulk heterojunction organic solar cells using these BODIPY-based small molecules as electron donors along with fullerene derivative (PC 71 BM) and medium bandgap non-fullerene acceptor IDT-TC as electron acceptors. The optimized OSCs based on ZMH-1:PC 71 BM, ZMH-2:PC 71 BM, ZMH-1:IDT-IC, and ZMH-2:IDT-IC attain overall PCEs of 8.91%, 6.61%, 11.28%, and 5.48%, respectively. Moreover, when a small amount of PC 71 BM as guest acceptor is added to the binary host ZMH-1:IDT-TC and ZMH-2:IDT-TC, the ternary OSCs based on ZMH-1 and ZMH-2 reach PCEs of 13.70% and 12.71%, respectively.

The antimicrobial activity of new acid-functionalized porphyrins, with or without ultra-high irradiance, was investigated. Antibacterial efficacy was evaluated against Staphylococcus aureus (methicillin-resistant or methicillin-sensitive strains) and antifungal efficacy was evaluated against the yeast Candida albicans and the filamentous fungi Aspergillus fumigatus. Overall, the porphyrins tested are more effective against S. aureus. The best results were obtained with zinc diacid porphyrins 4 and 5 after only 3 min of ultra-high irradiation (500 mW/cm 2 , 405 nm), demonstrating that acid-functionalized porphyrins are promising as novel antimicrobial drugs for surface disinfection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Ground-state and time-dependent density functional theory (TDDFT) calculations with the long-range-corrected, Coulomb-attenuating CAMY-B3LYP exchange-correlation functional and large, all-electron STO-TZ2P basis sets have been used to examine the potential "inverse hypercorrole" character of meso-p -nitrophenyl-appended dicyanidocobalt(III) corrole dianions. The effect is most dramatic for 5,15-bis( p -nitrophenyl) derivatives, where it manifests itself in intense NIR absorptions. The 10-aryl groups in these complexes play a modulatory role, as evinced by experimental UV-visible spectroscopic and electrochemical data for a series of 5,15-bis( p -nitrophenyl) dicyanidocobalt(III) corroles. TDDFT (CAMY-B3LYP) calculations ascribe these features clearly to a transition from the corrole's a 2u -like HOMO (retaining the D 4h irrep used for metalloporphyrins) to a nitrophenyl-based LUMO. The outward nature of this transition contrasts with the usual phenyl-to-macrocycle direction of charge transfer transitions in many hyperporphyrins and hypercorroles; thus, the complexes studied are aptly described as inverse hypercorroles.

A mono-DMSO cobalt meso -CF 3 corrole, formulated as (CF 3 ) 3 CorCo(DMSO), where (CF 3 ) 3 Cor is the trianion of 5,10,15-tris(trifluoromethyl)corrole, was synthesized and characterized as to its spectral and electrochemical properties in nonaqueous media with a focus on its coordination chemistry and electronic structure. Cyclic voltammetric measurements showed more facile reductions and difficult oxidations compared to the cobalt triarylcorrole possessing p -CF 3 Ph units at the meso -positions, a result consistent with the enhanced inductive effect of the electron-withdrawing trifluoromethyl substituents linked directly at the meso -carbon atoms of the macrocycle. The effects of DMSO, pyridine, and cyanide anions (CN - ) on the electrochemistry and spectral properties of the compound were investigated, and it was found that only two molar equivalents are needed to form the bis-CN adduct, which exhibited two 1-electron oxidations at 0.27 and 0.95 V vs saturated calomel electrode (SCE) in CH 2 Cl 2 /0.1 M TBAP. The sites of electron transfer in the first oxidation and reduction were investigated by spectroelectrochemistry and confirmed that the first electron addition affords a Cor 3- Co II complex under all solution conditions independent of the initial coordination and/or electronic configuration ( i.e ., innocent Cor 3- Co III or noninnocent Cor •2- Co II ). In contrast, data for the first oxidation suggests that the site of electron abstraction (ligand or metal) depended upon coordination of the neutral and in situ generated complexes under the various solution conditions, leading to a Co(IV)-corrole 3- product for both the bis-pyridine and bis-cyanide adducts.

A novel cobalt corrole bearing 4-vinylphenyl groups at the 5,10,15- meso -positions of the macrocycle has been synthesized from tris(4-bromophenyl)corrole using a Suzuki coupling reaction. The spectral and electrochemical properties are reported in CH 2 Cl 2 along with its ability to form a highly stable six-coordinate complex and cross-linked corrole-based polymer in a 59% yield.

Herein, we report the synthesis and evaluation of carboxylic acid corroles bearing either one, two, three of four carboxylic groups as gram-positive antibacterial agents against two strains of S. aureus, one methicillin-sensible (MSSA) and the other methicillin-resistant (MRSA). Lead compounds 5 and 6 show low minimum inhibitory concentrations (MICs) of 0.78 μg/mL against both MSSA and MRSA. These molecules, previously underexplored as antibacterial agents, can now serve as a new scaffold for antimicrobial development., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

A series of cobalt nitrophenylcorroles were spectrally characterized in CH 2 Cl 2 , and under certain solution conditions, several compounds were shown to exhibit hypercorrole spectra resulting from charge transfer interactions from the corrole π-system to the redox-active meso -NO 2 Ph substituents. The resulting spectral pattern has not previously been reported for metallocorroles and in the case of the cobalt derivatives was shown to depend upon the number and position of the meso -nitrophenyl groups on the macrocycle, the position of the NO 2 substituent on the meso -phenyl ring(s) ( para or meta ), and the electronic structure of the corrole, which can exist in its innocent or noninnocent form depending in large part upon the type and number of axial ligands. Cobalt corroles bearing p -nitrophenyl groups at the 5,15- or 5,10,15-positions of the macrocycle exhibited the most marked hypercorrole spectra under solution conditions where the complex was innocent (i.e., Cor 3- Co III ), and a systematic analysis of the spectral data suggests the root of this perturbation to be a corrole-to-aryl interaction (i.e., ligand-to-ligand charge transfer or LLCT). The largest interaction between the π-system and the NO 2 Ph substituents was seen upon coordination of anionic cyanide (CN - ) axial ligands to the Co(III) center of the bis-(CN - )-5,15-dinitrophenyl derivative, resulting in a cobalt hypercorrole spectrum where the broad Q-band was red-shifted even further into the NIR region and located at 795 nm in CH 2 Cl 2 and 827 nm in pyridine. Cyclic voltammetry of the bis-CN - adducts showed that the first electrons are added to the LUMOs of the p -NO 2 Ph substituents rather than the corrole, while the same orbitals for the mono-CN - adducts are nearly degenerate. This redox behavior contrasts with what is seen for the noninnocent nitrophenyl corroles having "normal" unperturbed UV-vis spectra where the first reduction involves the π-system of the macrocycle, followed by reduction of the p -NO 2 Ph groups at more negative potentials.

Corrole chemistry has witnessed an impressive boost in studies in the last 20 years, thanks to the possibility of preparing corrole derivatives by simple synthetic procedures. The investigation of a large number of corroles has highlighted some peculiar characteristics of these macrocycles, having features different from those of the parent porphyrins. With this progress in the elucidation of corrole properties, attention has been focused on the potential for the exploitation of corrole derivatives in different important application fields. In some areas, the potential of corroles has been studied in certain detail, for example, the use of corrole metal complexes as electrocatalysts for energy conversion. In some other areas, the field is still in its infancy, such as in the exploitation of corroles in solar cells. Herein, we report an overview of the different applications of corroles, focusing on the studies reported in the last five years.

The quest for small molecules that strongly bind to G-quadruplex-DNA (G4), so-called G4 ligands, has invigorated the G4 research field from its very inception. Massive efforts have been invested to discover or rationally design G4 ligands, evaluate their G4-interacting properties in vitro through a series of now widely accepted and routinely implemented assays, and use them as innovative chemical biology tools to interrogate cellular networks that might involve G4s. In sharp contrast, only uncoordinated efforts aimed at developing small molecules that destabilize G4s have been invested to date, even though it is now recognized that such molecular tools would have tremendous application in neurobiology as many genetic and age-related diseases are caused by an overrepresentation of G4s. Herein, we report on our efforts to develop in vitro assays to reliably identify molecules able to destabilize G4s. This workflow comprises the newly designed G4-unfold assay, adapted from the G4-helicase assay implemented with Pif1, as well as a series of biophysical and biochemical techniques classically used to study G4/ligand interactions (CD, UV-vis, PAGE, and FRET-melting), and a qPCR stop assay, adapted from a Taq -based protocol recently used to identify G4s in the genomic DNA of Schizosaccharomyces pombe . This unique, multipronged approach leads to the characterization of a phenylpyrrolocytosine (PhpC)-based G-clamp analog as a prototype of G4-disrupting small molecule whose properties are validated through many different and complementary in vitro evaluations.

A series of 43 antiviral corrole-based molecules have been tested on myxoma virus (Lausanne-like T1MYXV strain). An autofluorescent MYXV, with an ANCHOR cassette, has been used for the studies. A 2 B-fluorocorroles display various toxicities, from 40 being very toxic (CC 50 = 1.7 μM) to nontoxic 38 (CC 50 > 50 μM), whereas A 3 -fluorocorroles, with one to three fluorine atoms, are not toxic (with the exception of corroles 9 , 10 , and 22 ). In vitro , these compounds show a good selectivity index when used alone. Corrole 35 seems to be the most promising compound, which displays a high selectivity index with the lowest IC 50 . Interestingly, this "Hit" corrole is easy to synthesize in a two-step reaction. Upscaling production up to 25 g has been carried out for in vivo tests. In vivo studies on New Zealand white rabbits infected with myxoma virus show that symptoms are delayed and animal weight is increased upon treatment, while no acute toxicity of the corrole molecule was detected.

Despite the wide use of magnetic resonance imaging (MRI) as a clinical diagnostic tool, there are still no clinically approved MRI contrast agents that can be applied for cerebral Alzheimer's disease (AD) biomarker imaging. We report here the design and development of the first amyloid-β (Aβ)-targeted, blood-brain barrier (BBB) penetrable theranostic Gd(DOTA)-cyanine dyad, which was synthesized by the conjugation of Gd(DOTA) complex and carbazole-based cyanine dye by the copper(I)-catalyzed azide-alkyne cycloaddition click reaction for imaging of Aβ in vivo and ex vivo in AD mouse models. This dyad, as a multimodal probe, possesses desirable multifunctional properties, including good biocompatibility, low cytotoxicity, high Aβ selectivity, strong fluorescence enhancement upon binding with Aβ species, good paramagnetic properties, high stability, good BBB penetrability, and fast elimination from the mouse. The longitudinal relaxivity ( r 1 ) of the dyad was found to be 4.42 mM -1 s -1 at 3 T, suggesting it to be promising as a T 1 -weighted MRI contrast agent. The probe has been successfully demonstrated to be able to be applied for one- and two-photon excited fluorescence and magnetic resonance (MR) imaging of Aβ in transgenic mouse models of AD. In addition, it can inhibit Aβ aggregation, protect against toxicity induced by Aβ, and suppress Aβ-induced reactive oxygen species (ROS) production. Our results demonstrate the highly promising theranostic capability of the dyad for diagnosis and therapy of AD and extraordinary potential for MRI of Aβ in humans.

Two mitochondrial-targeted fluorescent probes, 2 and 3, based on a BODIPY scaffold and one or two piperidinyl groups were easily synthesized by Knoevenagel condensation. The biological imaging applications of the two probes 2 and 3 in live HepG2 cells reveal that these two probes display excellent mitochondrial imaging ability. Thus, these probes appear as promising tools for visualization of mitochondrial within live cells., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interests., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The quantification of specific gases among thousands of VOCs (Volatile Organic Compounds) present in the human breath at the ppm/ppb level can be used to evidence the presence of diseases in the human body. The detection of these biomarkers in human exhaled breath through a noninvasive approach is an important field of research that is still attracting significant attention to this day. A portable device working at room temperature and usable directly on exhaled breath samples is still a challenge requiring a sensing material with high performances. The rich composition of the human breath implies that the sensing material must be highly selective and sensitive (ppm/ppb) in high relative humidity (RH) conditions and preferably at room temperature. The present work intends to provide a review on recent works in this application field through the use of porous materials and discuss the importance of Metal Organic Frameworks (MOFs) for such application. MOFs are highly porous crystalline materials often used for gas detection and capture, thus raising questions about their potential for detection in exhaled breath.

A series of "N 2 O 2 -type" manganese dipyrrin-bisphenols (DPP), formulated as (Ar)DPPMn, where Ar = pentafluorophenyl (F 5 Ph), phenyl (Ph), or mesityl (Mes), were electrochemically and spectroscopically characterized in nonaqueous media with and without added anions in the form of tetrabutylammonium salts (TBAX where X = ClO 4 - , PF 6 - , BF 4 - , F - , Cl - , OH - , or CN - ). Two major one-electron reductions are observed under most solution conditions, the first of which is assigned as a Mn III/II process and the second as electron addition to the π-ring system as confirmed by spectroelectrochemistry. Each Mn III complex also exhibits one or two one-electron oxidations, the exact number depending upon the positive potential limit of the electrochemical solvent. The two oxidations are separated by 580-590 mV in CH 3 CN containing 0.1 M TBAPF 6 and are assigned as π-ring-centered electron transfers to stepwise form a (Ar)DPPMn III π-cation radical and dication under these solution conditions. Comparisons are made between redox properties of (Ar)DPPMn and manganese(III) porphyrins, corroles, and corrolazines each of which contains an innocent trianionic complexing ligand. The redox behavior and spectroscopic properties of [(Ar)DPPMn] n where n = 0, -1, or +1 are also compared to that of other structurally related [(Ar)DPPM] n complexes under similar solution conditions where M = Co II , Cu II , B III , or Au III .

Twenty-nine fluorinated corroles were prepared, spectroscopically characterized, and studied for their antiviral activity against human cytomegalovirus infection. Six corroles were also fully characterized by X-ray crystallography giving insights on their geometrical features. The halogenated corroles reported herein exhibit significantly improved antiviral activity over their non-halogenated counterparts and over nitro-corrole analogs previously reported. Full activity of thirteen A 3 -corroles is achieved with four fluorine atoms present on the meso -phenyl ring reaching a selectivity index above 300. The maximum activity is achieved for A 2 B-corroles with selectivity indexes above 400. We thus demonstrate that the fluorocorrole is a highly potent platform to synthesize a new generation of anti hCMV molecules., (This journal is © The Royal Society of Chemistry 2020.)

Three mono-CN ligated anionic cobalt A 3 -triarylcorroles were synthesized and investigated as to their spectroscopic and electrochemical properties in CH 2 Cl 2 , pyridine (Py), and dimethyl sulfoxide (DMSO). The newly synthesized corroles provide the first examples of air-stable cobalt corroles with an anionic axial ligand and are represented as [(Ar) 3 CorCo III (CN)] - TBA + , where Cor is the trivalent corrole macrocycle, Ar is p -(CN)Ph, p -(CF 3 )Ph, or p -(OMe)Ph, and TBA + is the tetra- n -butylammonium (TBA) cation. Multiple redox reactions are observed for each mono-CN derivative with a key feature being a more facile first oxidation and a more difficult first reduction in all three solvents as compared to all previously examined corroles with similar meso- and β-pyrrole substituents. Formation constants (log K ) for conversion of the five-coordinate mono-CN complex to its six-coordinate bis-CN form ranged from 10 2.8 for Ar = p -(OMe)Ph to 10 4.7 for Ar = p -(CN)Ph in DMSO as determined by spectroscopic methodologies. The in situ generated bis-CN complexes, represented as [(Ar) 3 CorCo III (CN) 2 ] 2- (TBA + ) 2 , and the mixed ligand complexes, represented as [(Ar) 3 CorCo III (CN)(Py)] - TBA + , were also investigated as to their electrochemical and spectroscopic properties. UV-visible spectra and electrode reactions of the synthesized mono-CN derivatives are compared with the neutral mono-DMSO cobalt corrole complexes and the in situ generated bis-CN and bis-Py complexes, and the noninnocent (or innocent) nature of each cobalt corrole system is addressed. The data demonstrate the ability of the CN - axial ligand(s) to stabilize the high-valent forms of the metallocorrole, leading to systems with innocent macrocyclic ligands. Although a number of six-coordinate cobalt(III) corroles with N-donor ligands were characterized in the solid state, a dissociation of one axial ligand readily occurs in nonaqueous solvents, and this behavior contrasts with the high stability of the currently studied bis-CN adducts in CH 2 Cl 2 , pyridine, or DMSO. Linear free energy relationships were elucidated between the meso -phenyl Hammett substituent constants (Σσ) and the measured binding constants, the redox potentials, and the energy of the band positions in the mono-CN and bis-CN complexes in their neutral or singly oxidized forms, revealing highly predictable trends in the physicochemical properties of the anionic corroles.

Human cytomegalovirus (hCMV) is responsible for several pathologies impacting immunocompromised patients and can trigger life-threatening infection. Several antivirals are available and are used in the clinic, but hCMV resistant strains have appeared and patients have encountered therapeutic failure. Hence, there is a constant need for new best in class or first in class antiviral molecules. We have previously shown that nitrocorroles could be used as a potent anti-hCMV agent without acute toxicity in mice. They therefore represent an excellent platform to perform structure-activity relationship (SAR) studies and to increase efficiency or reduce toxicity. We have generated original A 2 B- and A 3 -substituted nitrocorroles and have discovered optimized compounds with selectivity indices above 200. These compounds are easily synthesized in only one to two-step reactions; they are up-scalable and cost efficient. They are therefore excellent candidates for hCMV therapies and they pave the way for a new generation of molecules., (This journal is © The Royal Society of Chemistry 2020.)

Two BODIPY derivatives with one (B2) and two (B3) carbazole moieties were synthesized and applied as electron-donor materials in organic photovoltaic cells (OPV). Their optical and electrochemical properties were systematically investigated. These BODIPY dyes exhibit excellent solubility in organic solvents and present high molar extinction coefficients (1.37-1.48 × 10 5 M -1 cm -1 ) in solutions with absorption maxima at 586 nm for mono-styryl groups and at 672 nm for di-styryl groups. The introduction of the styryl moieties results in a large bathochromic shift and a significant decrease in the HOMO-LUMO energy-gaps. The BODIPY dyes show relatively low HOMO energies ranging from -4.99 to -5.16 eV as determined from cyclic voltammetry measurements. Cyclic voltammetry measurements and theoretical calculations demonstrate that the frontier molecular orbital levels of these compounds match with those of PC 71 BM as the acceptor, supporting their application as donor materials in solution-processed small molecule bulk heterojunction (BHJ) organic solar cells. After the optimization of the active layer, B2:PC 71 BM and B3:PC 71 BM based organic solar cells showed an overall power conversion efficiency of 6.41% and 7.47%, respectively. The higher PCE of the B3-based OSC is ascribed to the more balanced charge transport and exciton dissociation, better crystallinity and molecular packing.

BACKGROUND: An estimated 30% to 50% of people with a mental illness also have a substance use problem. Referred to as having a dual diagnosis, these patients experience high levels of unmet needs, poor health outcomes, and require specialized care during psychiatric hospitalization. Research on nursing inpatients with a dual diagnosis is limited and patient perceptions of helpful care during hospitalization are unknown. AIMS: What nursing interventions, attitudes, actions, and/or behaviors are perceived as helpful by patients with a dual diagnosis during psychiatric hospitalization? METHODS: A qualitative-descriptive design was used. Twelve adult inpatients with a dual diagnosis were recruited using purposive sampling. Individual, semistructured interviews were conducted, and interview data were analyzed using content analysis. RESULTS: Helpful nursing occurred across three themes: (1) promoting health in everyday living, (2) managing substance use in tandem with mental illness, and (3) building therapeutic relationships. CONCLUSIONS: Specific examples of helpful interventions and their reported outcomes reinforce the critical role that nurses play in the health and recovery of inpatients with a dual diagnosis. The importance of collaborative, strengths-based approaches is highlighted, and expanding the nurse's role to include evidence-based responses to substance use is recommended.

A new series of cobalt A 3 -triarylcorroles were synthesized and the compounds examined as to their electrochemical and spectroscopic properties in CH 2 Cl 2 or dimethyl sulfoxide (DMSO) containing 10 different anions added to the solution in the form of tetrabutylammonium salts. The investigated anions were PF 6 - , BF 4 - , HSO 4 - , ClO 4 - , Br - , I - , Cl - , OAc - , F - , OTs - , and CN - , all but three of which were found to facilitate reduction of the cobalt corrole in dilute CH 2 Cl 2 solutions, as determined by a combination of UV-vis spectroscopy and spectroelectrochemistry. The synthesized corroles are represented as (Ar) 3 CorCo(DMSO), where Ar is a meso -phenyl group containing one of 10 different electron-donating or -withdrawing substituents. The axial DMSO ligand was found to dissociate in dilute (10 -5 M) CH 2 Cl 2 solutions, but this was not the case at the higher electrochemical concentration of 10 -3 M, where the investigated corroles exhibit a rich redox reactivity, undergoing up to five reversible one-electron-transfer reactions under the different solution conditions. The reversible half-wave potentials for generation of the singly oxidized corroles varied by over 1.0 V with a change in the electron-donating or -withdrawing meso -phenyl substituents and type of anion added to the solution, ranging from E 1/2 = 0.83 V in one extreme to -0.42 V in the other. Much smaller shifts in the potentials (on the order of ∼210 mV) were observed for the reversible first reduction as a function of changes of the anion and/or corrole substituents, with the only exception being in the case of CN - , where the E 1/2 values in CH 2 Cl 2 ranged from +0.08 V in solutions containing 0.1 M TBAClO 4 to >-1.8 V upon the addition of CN - .

Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin-bisphenolate (DPP) complexes, we synthesized the gold(iii) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that the ground states of the new complexes indeed correspond to an innocent Au III -DPP 3- , paralleling a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand-centered oxidations, reduction of AuDPP is predicted to occur across both the metal and the ligand., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Porous organic polymers (POPs), known for their high surface area and porosity, were prepared starting from tetraphenyl tetrahedral-shaped building blocks and corrole macrocyclic linkers either as free bases or cobalt complexes. This synthetic method allowed us to construct new porous frameworks with high carbon monoxide adsorption properties. Two synthetic strategies were developed for incorporating cobalt corroles into the porous matrix. The first method is based on the copper-free Sonogashira cross-coupling reaction between a free base diodo-corrole with a tetrahedral shaped derivative followed by cobalt complexation of the resulting material, leading to POP-CorCo-1. The second strategy consists of preparing POP-CorCo-2 by directly using in the coupling reaction the metalated cobalt corrole temporarily protected by two ammine ligands at the axial position. The design principles as well as the relationship between the structure and the selective CO adsorption performance are presented. The adsorption capacities and selectivities of CO were calculated from a multisite Langmuir isotherm model and using IAST theory. Spectroscopic studies (NMR, FTIR, UV-visible), kinetic sorption measurements and microscopic analyses made possible to provide a fairly complete description of the structure of the POPs, their porosity and the nature of solid-gas interactions. The POPs prepared by both methods show a high permanent porosity and outstanding CO sorption properties with a high selectivity over N2, O2 and CO2, up to 15 700, 4000 and 1800, respectively. The two POP-CorCo therefore offer confined molecular spaces for ascertaining a high accessibility of the metallocorrole active sites for gas binding on the cobalt atom, thus featuring high potential for applications in selective capture or sensing of CO versus N2, O2 and CO2.

The self-assembly of functional molecules into uniform nanostructures with innovational properties has attracted extensive research interest. In the present work, the assembly structures and electronic properties of a novel type of truxene derivative, e.g. truxene-porphyrin derivatives, were studied, for the first time, on a highly oriented pyrolytic graphite (HOPG) surface. Scanning tunneling microscopy (STM) images revealed that the truxene-porphyrin compounds could be parallelly arranged into long-ranged lamellar patterns. Density functional theory (DFT) calculations helped explain the assembly mechanisms further. Besides, order distribution of the smaller compound 1T1P in the 1,3,5-tris(10-carboxydecyloxy)-benzene (TCDB) host network was achieved, which is a reflection of the dimensional effect in the host-guest assembly. Furthermore, together with theoretical analyses, scanning tunneling spectroscopy (STS) measurements were conducted to investigate the electronic properties of truxene-porphyrin compounds. Results showed that the metalation of the porphyrin units could have a significant effect on the band gap and the position of the gap center. The study enhances our understanding of the assembly mechanism of truxene derivatives at the molecular level and paves the way towards fabricating truxene-based functional nanodevices.

Three cobalt dipyrrin-bisphenol (DPPCo) complexes with different meso-aryl groups (pentafluorophenyl, phenyl, and mesityl) were synthesized and characterized based on their electrochemistry and spectroscopic properties in nonaqueous media. Each DPPCo undergoes multiple oxidations and reductions with the potentials, reversibility, and number of processes depending on the specific solution conditions, the specific macrocyclic substituents, and the type and number of axially coordinated ligands on the central cobalt ion. Theoretical calculations of the compounds with different coordination numbers are given in the current study in order to elucidate the cobalt-ion oxidation state and the innocence or noninnocence of the macrocyclic ligand as a function of the changes in the solvent properties and degree of axial coordination. Electron paramagnetic resonance spectra of the compounds are obtained to experimentally assess the electron spin state. An X-ray structure of the six-coordinate complex is also presented. The investigated chemical properties of DPPCo compounds under different solution conditions are compared to those of cobalt corroles, where the macrocycle and metal ion also possess formal 3- and 3+ oxidation states in their air-stable forms.

A series consisting of a dyad, a triad and a tetrad containing either two, three and four BODIPY units, respectively, has been synthesized and fully characterized and compared to two mono-BODIPY analogs (used as references). The one- and two-photon photophysical properties have been measured and the X-ray structures of four of the BODIPY derivatives have been determined. In the 700-900 nm range, the two-photon absorption (TPA) cross sections range from 30 GM to 160 GM for these compounds., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles. The proposed electronic configurations of the initial compounds and the prevailing redox reactions involving the electroactive central cobalt ion, the electroactive conjugated macrocycle, and the electroactive meso-nitrophenyl groups are all discussed in terms of solvent binding and the number of the nitrophenyl groups and other substituents on the meso-nitrophenyl rings of the compounds.

Low bandgap A-π-D copolymer, P(BdP-DEHT), consisting of alternating BOronDIPYrromethene (BODIPY) and thiophene units bridged by ethynyl linkers, and its porphyrin-enriched analogue, P(BdP/Por-DEHT), were prepared, and their optical and electrochemical properties were studied. P(BdP-DEHT) exhibits strong absorption in the 500-800 nm range with an optical bandgap of 1.74 eV. On the basis of cyclic voltammetry, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels are evaluated to be -5.40 and -3.66 eV, respectively. After the anchoring of zinc(II) porphyrin on the BODIPY unit, P(BdP/Por-DEHT) displays broadened absorption, thanks to porphyrins, and the optical bandgap decreases to 1.59 eV because of extension of BODIPY conjugation. The resulting estimated HOMO and LUMO energy levels, respectively, move to -5.32 and -3.73 eV. After optimization of the P(BdP-DEHT) or P(BdP/Por-DEHT) to PC 71 BM weight ratio to 1:2 in dichlorobenzene solution, the bulk heterojunction polymer solar cells show overall power conversion efficiencies (PCEs) of 3.03 and 3.86%, respectively. After solvent vapor annealing (SVA) treatment in CH 2 Cl 2 for 40 s, the PCEs increased to 7.40% [V oc of 0.95 V, J sc of 12.77 mA/cm 2 , and fill factor (FF) of 0.61 with energy loss of 0.79 eV] and 8.79% (V oc of 0.92 V, J sc of 14.48 mA/cm 2 , and FF of 0.66 with energy loss of 0.67 eV). The increase in the PCE for P(BdP/Por-DEHT)-based devices is mainly attributed to the enhancement in J sc and FF, which may be related to the broader absorption spectra, lower band gap, and better charge transport of P(BdP/Por-DEHT) compared to P(BdP-DEHT). This could also be related to the optimized nanoscale morphology of the active layer for both efficient exciton dissociation and charge transport toward the electrodes and a balanced charge transport in the device, induced by the SVA treatment of the active layer.

A series of open-chain pentapyrroles and sapphyrins with highly electron-withdrawing substituents (i.e., CN, CF 3 , or CO 2 Me) on the meso-phenyl rings was synthesized and characterized as to the spectral properties, protonation reactions, and electrochemistry in non-aqueous media. The investigated compounds are represented as (Ar) 4 PPyH 3 and (Ar) 4 SapH 3 where PPy and Sap correspond to the tri-anion of the open-chain pentapyrrole and sapphyrin, respectively, and Ar=p-CNPh, p-CF 3 Ph, or p-CO 2 MePh. UV/Vis and 1 H NMR spectroscopy as well as mass spectrometry data are given for the confirmation of the structures for the newly synthesized compounds. An X-ray structure for one of the pentapyrroles, that is, (p-CF 3 Ph) 4 PPyH 3 (2), is also presented. The protonation processes were examined by UV/Vis absorption spectroscopy during the titration of the compounds with trifluoroacetic acid (TFA) in CH 2 Cl 2 . Equilibrium constants for the protonation reactions were calculated by using both the Hill equation and the mole ratio method. The protonation-initiated conversion of pentapyrroles to sapphyrins upon oxidation was also investigated. Cyclic voltammetry was used to measure the redox potentials in CH 2 Cl 2 , PhCN, and/or pyridine (Py). Electrochemical properties, protonation constants, and chemical reactions of the six compounds in the two series were then analyzed as a function of the solvent properties and the type of the electron-withdrawing groups on the meso-phenyl rings., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The electrochemistry and spectroelectrochemistry of four tetrapositively charged and two tetranegatively charged porphyrins were characterized in two nonaqueous solvents (dimethyl sulfoxide and N,N-dimethylformamide) containing 0.1 M tetra-n-butylammonium perchlorate. The tetrapositively charged compounds are represented by the tetrapyridylporphyrins [TRPyPM] 4+ (X - ) 4 , where R is a methyl or [2-[2-(2-methoxy)ethoxy]ethoxy]ethyl group, M = Mn III I, Mn III Cl, Cu II , or Pd II , and X = I - or Cl - . The tetranegatively charged porphyrins are represented by the tetrasulfonato derivatives [TPPSMn(OAc)] 4- (NH 4 + ) 4 and [TArPSMn(OAc)] 4- (NH 4 + ) 4 , where Ar = 4-O-[2-[2-(2-methoxy)ethoxy]ethoxy]ethylphenyl. Up to seven electrons can be added to the tetrapyridyl porphyrins in three to five reversible reductions, while up to four electrons can be added to the tetrasulfonato derivatives in four reversible processes. Three types of electrochemical behaviors are observed for reduction of the pyridinium groups on the tetrapyridyl porphyrins. One is for the manganese(II) complexes where the four equivalent pyridinium groups are reduced in a single overlapping four-electron-transfer step. Another is for the free-base porphyrin, where four well-separated one-electron reductions occur, while the third is for copper(II) and palladium(II) derivatives, where reduction of the four pyridinium groups proceeds in two well-separated two-electron-transfer steps. The electrochemical and spectroelectrochemical properties were also characterized for a 1:1 mixture of the tetrapositively and tetranegatively charged manganese porphyrins to investigate possible interactions between these two species. An interaction between the two porphyrins was indeed observed in both solvents after electroreduction of the four pyridinium groups, which led to a substantial change in the mechanism for reduction of the pyridinium groups from an initial single overlapping four-electron-reduction process to two well-separated two-electron-transfer processes.

An original corrole-containing polyad for S 1 energy transfer, in which one zinc(II)-porphyrin donor is linked to two free-base corrole acceptors by a truxene linker, is reported. This polyad exhibits a rapid zinc(II)-porphyrin*→free-base corrole transfer (4.83×10 10  s -1 ; 298 K), even faster than the tautomerization in the excited state processes taking advantage of the good electronic communication provided by the truxene bridge. Importantly, the energy transfer process shows approximately 3-fold selectivity for one corrole N-H tautomer over the other even at low temperature (77 K). This selectivity is due to the difference in the J-integral being effective in both the Förster and Dexter mechanisms. The data are rationalized by DFT computations., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A porphyrin-diketopyrrolopyrrole-containing polymer (poly(porphyrin-diketopyrrolopyrrole) (PPDPP)) shows impressive molar absorption coefficients from λ=300 to 1000 nm. The photophysical and structural properties of PPDPP have been studied. With PPDPP as the electron donor and [6,6]-phenyl C 71 butyric acid methyl ester (PC 71 BM) as the electron acceptor, the bulk heterojunction polymer solar cell showed overall power conversion efficiencies of 4.18 and 6.44 % for as-cast and two-step annealing processed PPDPP:PC 71 BM (1:2) active layers, respectively. These results are quite impressive for porphyrin-containing polymers, especially when directly included in the π-conjugated backbone, and offer interesting perspectives for the design of new materials based on this chromophore., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Rules and regulations represent an aspect of psychiatric hospitalization about which little is known., Study Purpose: To explore the perceptions of rules from the perspective of youth receiving hospital-based psychiatric services., Design: Qualitative descriptive., Methods: Perceptions of rules were elicited through semi-structured interviews with a convenience sample of six youth., Results: Rules were perceived as governing virtually all aspects of everyday living in the hospital environment. Rules were used to structure daily activities, routines, and social interactions, and were embedded within clinical protocols and treatment plans. For each participant, "making sense" or "not making sense" were central themes through which rules were interpreted as being either therapeutic or oppressive. Rules that made "no sense" negatively affected youth mood, behavior, treatment adherence, and engagement in a collaborative relationship., Conclusion: Working in partnership with youth in psychiatric care to establish, implement, and evaluate rules that "make sense" can promote positive health outcomes and prevent negative, unintended consequences., (© 2017 Wiley Periodicals, Inc.)

The C3-symmetric cyclotriveratrylene (CTV) was covalently bonded via click chemistry to 1, 2, 3, and 6 zinc(II) porphyrin units to various host for C60. The binding constants, Ka, were measured from the quenching of the porphyrin fluorescence by C60. These constants vary between 400 and 4000 M(-1) and are considered weak. Computer modeling demonstrated that the zinc(II) porphyrin units, [Zn], exhibit a strong tendency to occupy the CTV cavity, hence blocking the access for C60 to land on this site. Instead, the pincer of the type [Zn]----[Zn] and in one case [Zn]----CTV, were found to be the most probable geometry to promote host-guest associations in these systems.

The synthesis of dyad and triad aza-BODIPY-porphyrin systems in two steps starting from an aryl-substituted aza-BODIPY chromophore is described. The properties of the resulting aza-BODIPY-porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The Cu(I)-catalysed Huisgen cycloaddition, known as "click" reaction, has been applied to the synthesis of a range of triazole-linked porphyrin/corrole to DOTA/NOTA derivatives. Microwave irradiation significantly accelerates the reaction. The synthesis of heterobimetallic complexes was easily achieved in up to 60% isolated yield. Heterobimetallic complexes were easily prepared as potential MRI/PET (SPECT) bimodal contrast agents incorporating one metal (Mn, Gd) for the enhancement of contrast for MRI applications and one "cold" metal (Cu, Ga, In) for future radionuclear imaging applications. Preliminary relaxivity measurements showed that the reported complexes are promising contrast agents (CA) in MRI.

Herein the synthesis, spectroscopic characterization, two-photon absorption and electrochemical properties of 3,6-disubstituted carbazole tweezers is reported. A dimer resulting from a Glaser homocoupling was isolated during a Sonogashira coupling reaction between a diethynyl-carbazole spacer and a 5-bromo-triarylporphyrin and the properties of this original compound were compared with the 3,6-disubstituted carbazole bisporphyrin tweezers. The dyads reported herein present a two-photon absorption maximum at 920 nm with two-photon absorption cross-section in the 1200 GM range. Despite a strong linear absorption in the Soret region and moderate fluorescence quantum yield, they both lead to a high brightness reaching 30 000 M(-1)  cm(-1) ., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Different nitroporphyrinoid derivatives were synthesized and studied as potential agents against human Cytomegalovirus. Interestingly, two nitrocorroles display strong activity against human Cytomegalovirus with IC 50 < 0.5 μM. These compounds also possess antiproliferative activities without detected in vivo toxicity. Therefore, nitrocorroles appear for the first time as potential active compounds that can be applied in human health.

Scientists are currently truly committed to enhance the specificity of chemotherapeutics that target DNA. To this end, sequence-specific drugs have progressively given way to structure-specific therapeutics. However, while numerous strategies have been implemented to design high-affinity candidates, strategies devoted to the design of high-selectivity ligands are still rare. Here we report on such an approach via the study of an amphiphilic compound, TEGPy, that self-assembles at a liquid/solid interface to provide nanosized objects that are stable in water. The resulting aggregates, identified through atomic force microscopy measurements, were found to disassemble upon interaction with DNA in a structure-specific manner (quadruplex- versus duplex-DNA). Our results provide a fertile ground for devising new strategies aiming at concomitantly enhancing DNA structural specificity and the water-solubility of aggregation-prone ligands.

Two new gold-phosphine-porphyrin derivatives were synthesized and fully characterized, and their photophysical properties investigated along a water-soluble analog. The cytotoxicity of the compounds was tested on cancer cells (HCT116 and SW480), and their cell uptake was followed by fluorescence microscopy in vitro (on SW480). The proof that the water-soluble gold-phosphine-porphyrin is a biologically active compound that can be tracked in vitro was clearly established, especially concerning the water-soluble analog. Some preliminary photodynamic therapy (PDT) experiments were also performed. They highlight a dramatic increase of the cytotoxicity when the cells were illuminated for 30 min with white light.

Secondary nucleic acid structures, such as DNA and RNA quadruplexes, are potential targets for cancer therapies. Ligands that interact with these targets could thus find application as anticancer agents. Synthetic G-quartets have recently found numerous applications, including use as bioinspired G-quadruplex ligands. Herein, the design, synthesis and preliminary biophysical evaluation of a new prototype multitarget G-quadruplex ligand, (PNA)PorphySQ, are reported, where peptidic nucleic acid guanine ((PNA)G) was incorporated in the porphyrin-templated synthetic G-quartet (PorphySQ). Using fluorescence resonance energy transfer (FRET)-melting experiments, PorphySQ was shown to possess enhanced quadruplex-interacting properties thanks to the presence of four positively charged (PNA)G residues that improve its electrostatic interactions with the binding site of both DNA and RNA quadruplexes (i.e., their negatively charged and accessible G-quartets), thereby making (PNA)PorphySQ an interesting prototype of a multitarget ligand. Both the chemical stability and water solubility of (PNA)PorphySQ are improved over the non-PNA derivative (PorphySQ), which are desirable properties for drug development, and while improvements remain to be made, this ligand is a promising lead for the further development of multitarget G-quadruplex ligands., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The antenna process from an energy donor (BODIPY; 4',4'-difluoro-1',3',5',7'-tetramethyl-4'-bora-3a',4a'-diaza-s-indacene) in its singlet state to two acceptors (two zinc(II) 5,15-p-tolyl-10-phenylporphyrin) bridged by a central truxene residue (5',5'',10',10'',15',15''-hexabutyltruxene), 5, has been analysed by means of comparison of the energy transfer rates with those of a structurally similar β-substituted BODIPY-(zinc(II) 5,10,15-p-tolyl-porphyrin), 6, where no conjugation is present between the donor and the two acceptors using the Förster resonance energy transfer (FRET) approximation. It is estimated that the energy transfer in operates mostly via a Dexter mechanism (>99%), and the remaining proceeds via a Förster mechanism (<1%). This information is useful for the design of future molecular devices aimed at harvesting light.

Red (no styryl), green (monostyryl), and blue (distyryl) BODIPY-gallium(III) (BODIPY = boron-dipyrromethene) corrole dyads have been prepared in high yields using click chemistry, and their photophysical properties are reported. An original and efficient control of the direction of the singlet energy transfers is reported, going either from BODIPY to the gallium-corrole units or from gallium-corroles to BODIPY, depending upon the nature of the substitution on BODIPY. In one case (green), both directions are possible. The mechanism for the energy transfers is interpreted by means of through-space Förster resonance energy transfer (FRET).

Template-assembled synthetic G-quartet (TASQ) has been reported recently as a G-quadruplex ligand interacting with DNA according to an unprecedented, nature-inspired 'like likes like' approach, based on the association between two G-quartets, one being native (quadruplex) and the other one artificial (ligand). Herein, a novel TASQ-based ligand is designed, synthesized and its quadruplex-recognition properties are evaluated in vitro: PorphySQ (for porphyrin-templated synthetic G-quartet) displays enhanced quadruplex recognition properties as compared to the very first reported prototype (DOTASQ, for DOTA-templated synthetic G-quartet), since the porphyrin template insures a more stable intramolecular G-quartet fold due to self-stabilizing interactions that may take place intramolecularly between the porphyrin ring and the formed G-quartet.

Nursing theories provide inspiration for practice by describing how to meet needs, enhance wellness, and respond to clients as whole persons. This paper discusses the McGill Model of Nursing with reference to how its ideas can support nursing practice for patients with cancer during the end-of-life phase. We suggest this model provides for a relational approach that is congruent with the philosophy of palliative care. The goal of this paper is to stimulate reflection amongst oncology nurses and nursing leaders. By comparing the value base of our practice against extant nursing theory, we may discover new opportunities for teaching and learning about what it means to be an end-of-life care nurse.

Novel zinc porphyrin tweezers in which two zinc porphyrins were connected with π-conjugated boron dipyrromethenes (BDP meso-Por(2) and BDP β-Por(2)) through triazole rings were synthesized to investigate the photoinduced energy transfer and electron transfer. The UV-vis spectrum of BDP β-Por(2) which has less bulky substituents than BDP meso-Por(2) exhibits splitting of the Soret band as a result of the interaction between porphyrins of BDP β-Por(2) in the excited state. Such interaction between porphyrins of both BDP β-Por(2) and BDP meso-Por(2) is dominant at room temperature, while the coordination of the nitrogen atoms of the triazole rings to the zinc ions of the porphyrins occurs at low temperature. The conformational change of the BDP-porphyrin composites was confirmed by the changes in UV-vis and fluorescence spectra depending on temperature. Photodynamics of BDP meso-Por(2) and BDP β-Por(2) has also been investigated by laser flash photolysis. Efficient singlet-singlet energy transfer from the ZnP to the π-conjugated BDP moiety of both BDP meso-Por(2) and BDP β-Por(2) occurred in opposite direction as compared to energy transfer from conventional BDP to ZnP due to the π-conjugation in nonpolar toluene. In polar benzonitrile, however, additional electron transfer occurred along with energy transfer., (© 2012 American Chemical Society)