Cobaltabis(Dicarbollide) [-COSAN] for Boron Neutron Capture Therapy of Head and Neck Cancer: Biodistribution and Irradiation Studies in an Experimental Oral Cancer Model.

Background: Boron neutron capture therapy (BNCT) is a tumor-selective particle radiotherapy that combines preferential boron accumulation in tumors and neutron irradiation. Based on previous studies in tumor-bearing mice, this study evaluated the biodistribution of the sodium salt of cobaltabis(dicarbollide) (Na[3,3'-Co(CBH)], abbreviated as Na[-COSAN]) in the hamster cheek pouch oral cancer model and the Na[-COSAN]/BNCT therapeutic effect on tumors and induced radiotoxicity. The synthesis and comprehensive characterization of B-enriched trimethylammonium salt of -[7,8-CBH]-carborane, along with the cesium and sodium salts of [-COSAN] cobaltabis(dicarbollide) are reported here for the first time.

Compelling DNA intercalation through 'anion-anion' anti-coulombic interactions: boron cluster self-vehicles as promising anticancer agents.

Anticancer drugs inhibit DNA replication by intercalating between DNA base pairs, forming covalent bonds with nucleotide bases, or binding to the DNA groove. To develop safer drugs, novel molecular structures with alternative binding mechanisms are essential. Stable boron hydrides offer a promising alternative for cancer therapy, opening up additional options like boron neutron capture therapy based on B and thermal neutron beams or proton boron fusion therapy using B and proton beams.

Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water.

A new cooperative photoredox catalytic system, [Ru(trpy)(bpy)(HO)][3,3'-Co(8,9,12-Cl-1,2-CBH)], , has been synthesized and fully characterized for the first time. In this system, the photoredox catalyst [3,3'-Co(8,9,12-Cl-1,2-CBH)], a metallacarborane, and the oxidation catalyst [Ru(trpy)(bpy)(HO)], are linked by non-covalent interactions. This compound, along with the one previously synthesized by us, [Ru(trpy)(bpy)(HO)][(3,3'-Co(1,2-CBH)], 4, are the only examples of cooperative molecular photocatalysts in which the catalyst and photosensitizer are not linked by covalent bonds.

The Rise of Boron-Containing Compounds: Advancements in Synthesis, Medicinal Chemistry, and Emerging Pharmacology.

Boron-containing compounds (BCC) have emerged as important pharmacophores. To date, five BCC drugs (including boronic acids and boroles) have been approved by the FDA for the treatment of cancer, infections, and atopic dermatitis, while some natural BCC are included in dietary supplements. Boron's Lewis acidity facilitates a mechanism of action via formation of reversible covalent bonds within the active site of target proteins.

Enhancing Photoredox Catalysis in Aqueous Environments: Ruthenium Aqua Complex Derivatization of Graphene Oxide and Graphite Rods for Efficient Visible-Light-Driven Hybrid Catalysts.

A ruthenium aqua photoredox catalyst has been successfully heterogeneneized on graphene oxide (GO@trans-fac-) and graphite rods (GR@trans-fac-) for the first time and have proven to be sustainable and easily reusable systems for the photooxidation of alcohols in water, in mild and green conditions. We report here the synthesis and total characterization of two Ru(II)-polypyridyl complexes, the chlorido trans-fac-[RuCl(bpea-pyrene)(bpy)](PF) (trans-fac-) and the aqua trans-fac-[Ru(bpea-pyrene)(bpy)OH](PF) (trans-fac-), both containing the -tridentate, 1-[bis(pyridine-2-ylmethyl)amino]methylpyrene (bpea-pyrene), and 2,2'-bipyridine (bpy) ligands. In both complexes, only a single isomer, the trans-fac, has been detected in solution and in the solid state.

Exploring the Role of Metal in the Biointeraction of Metallacarboranes with C. elegans Embryos.

Cobaltabis(dicarbollides), ferrabis(dicarbollide), and their halogenated derivatives are the most studied metallacarboranes with great medical potential. These versatile compounds and their iodinated derivatives can be used in chemotherapy, radiotherapy, particle therapy, and bioimaging when isotopes are used. These metallacarboranes have been evaluated in vitro and recently in vivo with complex animal models.

How a few help all: cooperative crossing of lipid membranes by COSAN anions.

Experimental results show that the presence of a concentration gradient of certain nano-ions (most notably cobaltabisdicarbollide ([-COSAN] anions), induce a current across intact artificial phospholipid bilayers in spite of the high Born free energy estimated for these ions. The mechanism underlying this observed translocation of nano-anions across membranes has yet to be determined. Here we show, using molecular dynamics simulations, that the permeation of [-COSAN] anions across a lipid bilayer proceeds in a cooperative manner.

Pioneering the Power of Twin Bonds in a Revolutionary Double Bond Formation. Unveiling the True Identity of o-Carboryne as o-Carborene.

The homolytic elimination of two H atoms from two adjacent carbons in benzene results in the aromatic product o-benzyne. In a similar way, the homolytic elimination of two H atoms from the two adjacent carbons in 1,2-C B H results in the aromatic product o-carboryne. In this work, we provide experimental and computational evidences that despite the similarity of o-carboryne and o-benzyne, the nature of the C-C bond generated between two adjacent carbons that lose H atoms is different.

Single stop analysis of a protein surface using molecular probe electrochemistry.

Visualization of a protein in its native form and environment without any interference has always been a challenging task. Contrary to the assumption that protein surfaces are smooth, they are in fact highly irregular with undulating surfaces. Hence, in this study, we have tackled this ambiguous nature of the 'surface' of a protein by considering the 'effective' protein surface (EPS) with respect to its interaction with the geometrically well-defined and structurally inert anionic molecule [3,3'-Co(1,2-CBH)], abbreviated as [-COSAN], whose stability, propensity for amine residues, and self-assembling abilities are well reported.

Probing electrophysiological activity of amphiphilic Dynorphin A in planar neutral membranes reveals both ion channel-like activity and neuropeptide translocation.

Dynorphin A (DynA) is an endogenous neuropeptide that besides acting as a ligand of the κ-opioid receptor, presents some non-opioid pathophysiological properties associated to its ability to induce cell permeability similarly to cell-penetrating peptides (CPPs). Here, we use electrophysiology experiments to show that amphiphilic DynA generates aqueous pores in neutral membranes similar to those reported previously in charged membranes, but we also find other events thermodynamically incompatible with voltage-driven ion channel activity (i.e.

Biomimetic Photodegradation of Glyphosate in Carborane-Functionalized Nanoconfined Spaces.

The removal of organophosphorus (OP) herbicides from water has been studied using adsorptive removal, chemical oxidation, electrooxidation, enzymatic degradation, and photodegradation. The OP herbicide glyphosate (GP) is one of the most used herbicides worldwide, leading to excess GP in wastewater and soil. GP is commonly broken down in environmental conditions to compounds such as aminomethylphosphonic acid (AMPA) or sarcosine, with AMPA having a longer half-life and similar toxicity to GP.

Towards the Application of Purely Inorganic Icosahedral Boron Clusters in Emerging Nanomedicine.

Traditionally, drugs were obtained by extraction from medicinal plants, but more recently also by organic synthesis. Today, medicinal chemistry continues to focus on organic compounds and the majority of commercially available drugs are organic molecules, which can incorporate nitrogen, oxygen, and halogens, as well as carbon and hydrogen. Aromatic organic compounds that play important roles in biochemistry find numerous applications ranging from drug delivery to nanotechnology or biomarkers.

A Potential Boron Neutron Capture Therapy Agent Selectively Suppresses High-Grade Glioma: and Exploration.

Glioblastoma (GBM), as the most central nervous system (CNS) intractable disease, has spoiled millions of lives due to its high mortality. Even though several efforts have been made, the existing treatments have had limited success. In this sense, we studied a lead compound, the boron-rich selective epidermal growth factor receptor (EGFR)-inhibitor hybrid , as a potential drug for GBM treatment.

Selective Antibody-Free Sensing Membranes for Picogram Tetracycline Detection.

As an antibody-free sensing membrane for the detection of the antibiotic tetracycline (TC), a liquid PVC membrane doped with the ion-pair tetracycline/θ-shaped anion [3,3'-Co(1,2-CBH)] ([-COSAN]) was formulated and deposited on a SWCNT modified gold microelectrode. The chosen transduction technique was electrochemical impedance spectroscopy (EIS). The PVC membrane was composed of: the tetracycline/[-COSAN] ion-pair, a plasticizer.

History of Cobaltabis(dicarbollide) in Potentiometry, No Need for Ionophores to Get an Excellent Selectivity.

This work is a mini-review highlighting the relevance of the θ metallabis(dicarbollide) [3,3'-Co(1,2-CBH)] with its peculiar and differentiating characteristics, among them the capacity to generate hydrogen and dihydrogen bonds, to generate micelles and vesicles, to be able to be dissolved in water or benzene, to have a wide range of redox reversible couples and many more, and to use these properties, in this case, for producing potentiometric membrane sensors to monitor amine-containing drugs or other nitrogen-containing molecules. Sensors have been produced with this monoanionic cluster [3,3'-Co(1,2-CBH)]. Other monoanionic boron clusters are also discussed, but they are much fewer.

Boron clusters (ferrabisdicarbollides) shaping the future as radiosensitizers for multimodal (chemo/radio/PBFR) therapy of glioblastoma.

Glioblastoma multiforme (GBM) is the most common and fatal primary brain tumor, and is highly resistant to conventional radiotherapy and chemotherapy. Therefore, the development of multidrug resistance and tumor recurrence are frequent. Given the poor survival with the current treatments, new therapeutic strategies are urgently needed.

New Boron Delivery Agents.

This proceeding article compiles current research on the development of boron delivery drugs for boron neutron capture therapy that was presented and discussed at the National Cancer Institute (NCI) Workshop on Neutron Capture Therapy that took place on April 20-22, 2022. The most used boron sources are icosahedral boron clusters attached to peptides, proteins (such as albumin), porphyrin derivatives, dendrimers, polymers, and nanoparticles, or encapsulated into liposomes. These boron clusters and/or carriers can be labeled with contrast agents allowing for the use of imaging techniques, such as PET, SPECT, and fluorescence, that enable quantification of tumor-localized boron and their use as theranostic agents.

3D and 2D aromatic units behave like oil and water in the case of benzocarborane derivatives.

A large number of 2D/2D and 3D/3D aromatic fusions that keep their aromaticity in the fused compounds have been synthesized. In addition, we have previously proven the electronic relationship between the 3D aromaticity of boron hydrides and the 2D aromaticity of PAHs. Here we report the possible existence of 3D/2D aromatic fusions that retain the whole aromaticity of the two units.

Water-Stable Carborane-Based Eu/Tb Metal-Organic Frameworks for Tunable Time-Dependent Emission Color and Their Application in Anticounterfeiting Bar-Coding.

Luminescent lanthanide metal-organic frameworks (Ln-MOFs) have been shown to exhibit relevant optical properties of interest for practical applications, though their implementation still remains a challenge. To be suitable for practical applications, Ln-MOFs must be not only water stable but also printable, easy to prepare, and produced in high yields. Herein, we design and synthesize a series of ( = 0-1) MOFs using a highly hydrophobic ligand CBL1: 1,7-di(4-carboxyphenyl)-1,7-dicarba--dodecaborane.

Water soluble organometallic small molecules as promising antibacterial agents: synthesis, physical-chemical properties and biological evaluation to tackle bacterial infections.

The Na[3,3'-Fe(8-I-1,2-CBH)] and Na[2,2'-M(1,7-CBH)] (M = Co, Fe) small molecules are synthesized and the X-ray structures of [(HO)(HO)][2,2'-Co(1,7-CBH)] and [Cs(MeCN)][8,8'-I-Fe(1,2 CBH)], both displaying a conformation of the [M(CB)] framework, are reported. Importantly, the supramolecular structure of [(HO)(HO)][2,2'-Co(1,7-CBH)] presents 2D layers leading to a lamellar arrangement of the anions while the cation layers form polymeric water rings made of six- and four-membered rings of water molecules connected OH⋯H hydrogen bonds; B-H⋯O contacts connect the cationic and anionic layers. Herein, we highlight the influence of the ligand isomers (-/-), the metal effect (Co/Fe) on the same isomer, as well as the influence of the presence of the iodine atoms on the physical-chemical and biological properties of these molecules as antimicrobial agents to tackle antibiotic-resistant bacteria, which were tested with four Gram-positive bacteria, five Gram-negative bacteria, and three strains that have been responsible for human infections.

Potential application of metallacarboranes as an internal reference: an electrochemical comparative study to ferrocene.

Ferrocene and its derivatives have been extensively used as an internal reference in electrochemical processes. Yet, they possess limitations such as solvent restrictions that require chemical modifications. In this regard, we have studied the use of metallacarboranes [3,3'-M(1,2-CBH)] (M = Co, Fe) as general internal reference systems and have proven their suitability by thoroughly investigating their electrochemical properties in both aqueous and organic electrolytes without any derivatization.

-Carborane-based fluorophores as efficient luminescent systems both as solids and as water-dispersible nanoparticles.

A set of -carborane-appended π-conjugated fluorophores and their light-emitting properties in the solid state are reported. The aggregation-induced emission enhancement (AIEE) exhibited for one of the fluorenyl derivatives paved the way to successfully preparing -carborane-containing organic nanoparticles (NPs) homogeneously dispersed in aqueous media that maintain their luminescence properties. Notably, NPs processed as thin films also show high fluorescence efficiency, suggesting potential optical and optoelectronic applications.