Triscyanocorrole, the Newest and Most Intriguing Member of the C-Substituted Corrole Family.

Considering the potential advantages of minimally sized corroles for diverse applications, this study reports a facile access to cyano-substituted derivatives via a rare CF/CN conversion. Investigation of the fully characterized gallium, phosphorus, and cobalt complexes discloses multiple effects of the meso-nitrile groups attached to the macrocycle. This corrole appears to be the most electron poor derivative which comes into play in the redox potentials of the corresponding complexes.

Co-occurrence of Traditional and Cyberbullying Victimization Among Adolescents: Characteristics, Psychological Difficulties, and Resilience.

This study examines whether students' experience of combined victimization, the experience of both traditional bullying and cyberbullying, is correlated with psychological difficulties. Additionally, the study examines whether Israeli students who cope with combined victimization differ in their resilience resources from students who experience solely traditional bullying, cyberbullying, or neither. Participants included 430 students aged 13-15 years from four Israeli schools who completed self-report questionnaires.

Redox Active Ligands for Catalyzing the Hydrogen Evolution Reaction.

Boron subphthalocyanines with chloride and fluoride axial ligands and three antimony complexes chelated by corroles that differ in size and electron-richness were examined as electrocatalysts for reduction of protons to hydrogen. Experiment- and computation-based investigations revealed that all redox events are ligand-centered and that the meso-C of the corroles and the peripheral N atoms of the subphthalocyanines are the largely preferred proton-binding sites.

Surprising Route to a Monoazaporphyrin and Full Characterization of Its Complexes with Five Different 3d Metals.

In the search for mild agents for the oxidative cyclization of tetrapyrromethane to the corresponding corrole, we discovered a route that leads to a monoazaporphyrin with three -CF groups. Optimization studies that allowed access to appreciable amounts of this new macrocycle paved the way for the preparation of its cobalt, copper, nickel, zinc, and iron complexes. All complexes were fully characterized by various spectroscopic methods and X-ray crystallography.

Diagnosis of chronic B-cell lymphoproliferative disease in peripheral blood = how machine learning may help to the interpretation of flow cytometry data.

Flow cytometry (FCM) has become a method of choice for immunologic characterization of chronic lymphoproliferative disease (CLPD). To reduce the potential subjectivities of FCM data interpretation, we developed a machine learning random forest algorithm (RF) allowing unsupervised analysis. This assay relies on 16 parameters obtained from our FCM screening panel, routinely used in the exploration of peripheral blood (PB) samples (mean fluorescence intensity values (MFI) of CD19, CD45, CD5, CD20, CD200, CD23, HLA-DR, CD10 in CD19-gated B cells, ratio of kappa/Lambda, and different ratios of MFI B-cells/T-cells [CD20, CD200, CD23]).

Reversible Reactions of Nitric Oxide with a Binuclear Iron(III) Nitrophorin Mimic.

Construction of functional synthetic systems that can reversibly bind and transport the most biologically important gaseous molecules, oxygen and nitric oxide (NO), remains a contemporary challenge. Myoglobin and nitrophorin perform these respective tasks employing a protein-embedded heme center where one axial iron site is occupied by a histidine residue and the other is available for small molecule ligation, structural features that are extremely difficult to mimic in protein-free environments. Indeed, the hitherto reported designs rely on sophisticated multistep syntheses for limiting access to one of the two axial coordination sites in small molecules.

Milestones and Most Recent Advances in Corrole's Science and Technology.

The renaissance in corrole chemistry is strongly correlated with synthetic breakthroughs that started in 1999, regarding the one-pot rather than multistep syntheses of this heme-like N4 macrocycle. This largely improved synthetic accessibility allowed for technological advances wherein the corresponding metal complexes have since been introduced as key elements. Great emphasis was devoted to the elucidation of the unique fundamental features that distinguish corrole ligands, among them outstanding electron donation (σ by the N atoms and π by the macrocycle) to transition metals chelated by them.

Hallmarks of anticancer and antimicrobial activities of corroles.

Corroles provide a remarkable opportunity for the development of cancer theranostic agents among other porphyrinoids. While most transition metal corrole complexes are only therapeutic, post-transition metallocorroles also find their applications in bioimaging. Moreover, corroles exhibit excellent photo-physicochemical properties, which can be harnessed for antitumor and antimicrobial interventions.

Supramolecular Control of Photonic Response and Sensing of Nitricoxide using Iron(III) Corrole Monolayers and Their Stacks.

In this work, we assemble amphiphilic iron(III) corroles at air-water interfaces into well-defined quasi-two-dimensional molecular monolayers and theirs stacks for sensing of nitric oxide (NO). For this purpose, we use the Langmuir-Blodgett (LB) technique, which allows varying the packing density of iron(III) corroles anchored to the aqueous subphase via one molecular side. The stacks of ten down to three molecular monolayers on the front and back sides of the substrates are sufficiently optically dense to detect NO binding to the layers photometrically.

Milestones in corrole chemistry: historical ligand syntheses and post-functionalization.

Corroles are synthetic porphyrin analogs that contain one carbon atom lesser and bear a trianionic N4 metal-chelating core. They require in-depth preparative chemistry, demonstrate unique coordination chemistry and have impressive and diverse physical properties, and these are commonly compared to their respective porphyrins. The corrole's macrocyclic system is inherently electron rich and chelates metal ions in a more compact, less symmetric tetranitrogen cavity compared to that of porphyrins.

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A nanoparticle-based system, composed of the gallium(III) complex of a minimally substituted corrole that is coated by transferrin as a targeting vehicle ( NPs), has been used for pre-clinical evaluation of its efficacy against human metastatic castration-resistant prostate cancer (mCRPC) tumor xenografts. All mice ( = 9) responded to a dose of 10 mg/kg, with a remarkable tumor growth inhibition of 400% following 2 weeks of treatment; Ames and hERG tests excluded potential concerns regarding mutagenicity and cardiotoxicity, respectively. Also demonstrated is the potential application of these NPs as sonodynamic agents for the preclinical treatment of pancreatic cancer.

Electronic Coupling and Electrocatalysis in Redox Active Fused Iron Corroles.

Conjugated arrays composed of corrole macrocycles are increasingly more common, but their chemistry still lags behind that of their porphyrin counterparts. Here, we report on the insertion of iron(III) into a β,β-fused corrole dimer and on the electronic effects that this redox active metal center has on the already rich coordination chemistry of [Htpfc] COT, where COT = cyclo-octatetraene and tpfc = tris(pentafluorophenyl)corrole. Synthetic manipulations were performed for the isolation and full characterization of both the 5-coordinate [Fetpfc(py)]COT and 6-coordinate [Fetpfc(py)]COT, with one and two axial pyridine ligands per metal, respectively.

Doubly Stimulated Corrole for Organelle-Selective Antitumor Cytotoxicity.

Balancing between safety and efficacy of cancer chemotherapeutics is achievable by relying on internal and/or external stimuli for selective and on-demand antitumor cytotoxicity. We now introduce the difluorophosphorus(V) corrole , a theranostic agent with a pH-sensitive -methylimidazole moiety. Structure/activity relationships, via comparison with the permanently charged and the lipophilic , uncovered the exceptional features of : nanoparticular and monomeric at neutral and low pH, respectively, 10-fold increased light-induced singlet oxygen production at acidic pH, internalization into malignant cells within minutes, and selective accumulation within lysosomes.

Corroles: The Hitherto Elusive Parent Macrocycle and its Metal Complexes.

Corroles, macrocycles that owe their name to the cobalt-chelating prosthetic group of vitamin B12 and share numerous features with the iron-chelating porphyrin present in heme proteins/enzymes, constantly cross new boundaries ever since stable derivatives became easily accessible. Particularly important is the increasing utilization of corroles and the corresponding metal complexes for the benefit of mankind, in terms of new drug candidates for treating various diseases and as catalysts for sustainable energy relevant processes. One challenge is to gain access to the plain macrocycle, as to allow for full elucidation of the most fundamental properties of corroles.

Ultrafast Electron Transfer in a Self-Assembling Sulfonated Aluminum Corrole-Methylviologen Complex.

Photoinduced electron transfer systems can mimic certain features of natural photosynthetic reaction centers, which are crucial for solar energy production. Among other tetra-pyrroles, the versatile chemical and photophysical properties of corroles make them very promising donors applicable in donor-acceptor complexes. Here, we present a first comprehensive study of ultrafast photoinduced electron transfer in a self-assembling sulfonated aluminum corrole-methylviologen complex combining visible and mid-IR transient absorption spectroscopy.

Hydrogen evolution catalysis by terminal molybdenum-oxo complexes.

Stable complexes with terminal triply bound metal-oxygen bonds are usually not considered as valuable catalysts for the hydrogen evolution reaction (HER). We now report the preparation of three conceptually different (oxo)molybdenum(V) corroles for testing if proton-assisted 2-electron reduction will lead to hyper-reactive molybdenum(III) capable of converting protons to hydrogen gas. The upto 670 mV differences in the [(oxo)Mo(IV)]/[(oxo)Mo(III)] redox potentials of the dissolved complexes came into effect by the catalytic onset potential for proton reduction thereby, significantly earlier than their reduction process in the absence of acids, but the two more promising complexes were not stable at practical conditions.

Comparison of manual statements from out-of-hospital trauma training programs and a national guideline on treatment of patients with severe and multiple injuries.

Purpose: Training programs help establish evidence-based knowledge in prehospital emergency care. This study aimed to compare manual statements from prehospital trauma training programs and evidence-based guidelines on treatment of patients with severe and multiple injuries.

Methods: A systematic comparison with the primary endpoint of the highest grades of recommendation (GoR A, "must") of the current version of the German guidelines and recent recommendations of the prehospital trauma training programs International Trauma Life Support (ITLS), Prehospital Trauma Life Support (PHTLS), and Traumamanagement (TM) based on their official textbooks was done.

Custom Tokenization Dictionary, CUSTODI: A General, Fast, and Reversible Data-Driven Representation and Regressor.

Custom tokenization dictionary (CUSTODI) is introduced as a novel way for tackling the problem of molecular representations, and especially the challenge of molecular property prediction. Herein, the motivational theory and the actual representation and model are presented and shown to have performance that is in line with benchmark methodologies. The uniqueness of CUSTODI is its applicability on small training sets and the developed theory suggests its possible use for a-priori estimation of future fit quality on any given dataset, regardless of the method used for fitting.

Solvent Effects on the Phosphorescence of Gold(III) Complexes Chelated by β-Multisubstituted Corroles.

A set of gold corrole complexes containing four different β-substituent groups (Br/I/CF), namely, , , and , were investigated; all showed room temperature phosphorescence. The phosphorescence quantum yields of the corroles were determined using tetraphenylporphyrin as a reference: Φ (, 0.75%) > Φ (, 0.

A Synthetic SOD/Catalase Mimic Compound for the Treatment of ALS.

Amyotrophic lateral sclerosis (ALS) is a progressive neurodegenerative disease affecting motor neurons. To date, the etiology of the disease is still unclear, with evidence of reactive oxygen species, mitochondrial dysfunction, iron homeostasis perturbation, protein misfolding and protein aggregation as key players in the pathology of the disease. Twenty percent of familial ALS and two percent of sporadic ALS instances are due to a mutation in Cu/Zn superoxide dismutase (SOD1).

Dimeric Corrole Analogs of Chlorophyll Special Pairs.

Chlorophyll special pairs in photosynthetic reaction centers function as both exciton acceptors and primary electron donors. Although the macrocyclic natural pigments contain Mg(II), the central metal in most synthetic analogs is Zn(II). Here we report that insertion of either Al(III) or Ga(III) into an imidazole-substituted corrole affords an exceptionally robust photoactive dimer.