Main advances in the application of scorpionate-based catalytic systems for the preparation of sustainable polymers.

Scorpionate ligands have emerged as pivotal components in the field of coordination chemistry and catalysis since the seminal work by Trofimenko in the late 1960s. These species have demonstrated an extraordinarily rich tridentate coordination chemistry, enhancing the stability of metal complexes. In addition, they offer the possibility of modifying the chemical and electronical features as κ-ligands, providing a wide variety of potential substrates with multiple donor atoms.

Exploring enantiopure zinc-scorpionates as catalysts for the preparation of polylactides, cyclic carbonates, and polycarbonates.

New and simple ligand design strategies for the preparation of versatile metal-based catalysts capable of operating under greener and eco-friendly conditions in several industrially attractive processes are in high demand for society development. We present the first nucleophilic addition of an organolithium to ketenimines which incorporates a stereogenic centre in an N-donor atom to prepare new enantiopure NNN-donor scorpionates. We have also verified its potential utility as a valuable scaffold for chirality induction through the preparation of inexpensive, non-toxic and asymmetric zinc complexes.

Evaluation of heteroscorpionate ligands as scaffolds for the generation of Ruthenium(II) metallodrugs in breast cancer therapy.

The modular synthesis of the heteroscorpionate core is explored as a tool for the rapid development of ruthenium-based therapeutic agents. Starting with a series of structurally diverse alcohol-NN ligands, a family of heteroscorpionate-based ruthenium derivatives was synthesized, characterized, and evaluated as an alternative to platinum therapy for breast cancer therapy. In vitro, the antitumoral activity of the novel derivatives was assessed in a series of breast cancer cell lines using UNICAM-1 and cisplatin as metallodrug control.

Very efficient organo-zinc scorpionates for CO fixation into a variety of cyclic carbonates: synthesis, coordination ability and catalytic studies.

The fixation of CO mediated by metal-based catalysts for the production of organic molecules of industrial interest such as cyclic carbonates is urgently required under green and eco-friendly conditions. Herein, we describe the easy preparation of sterically demanding scorpionate ligands bearing different electron-withdrawing groups, and their coordination ability for the preparation of robust zinc-based mononuclear complexes of the type [ZnMe(κ-NNN')] (4-6). These complexes, in combination with co-catalysts comprising larger ionic radius-based halides such as tetra--butylammonium, functioned as very active and selective catalysts for CO fixation into five-membered cyclic carbonates.

Synthesis, characterization, and antibacterial activities of a heteroscorpionate derivative platinum complex against methicillin-resistant .

is one of the species with the greatest clinical importance and greatest impact on public health. In fact, methicillin-resistant (MRSA) is considered a pandemic pathogen, being essential to develop effective medicines and combat its rapid spread. This study aimed to foster the translation of clinical research outcomes based on metallodrugs into clinical practice for the treatment of MRSA.

Enhanced Antitumoral Activity of Encapsulated BET Inhibitors When Combined with PARP Inhibitors for the Treatment of Triple-Negative Breast and Ovarian Cancers.

BRCA1/2 protein-deficient or mutated cancers comprise a group of aggressive malignancies. Although PARPis have shown considerably efficacy in their treatment, the widespread use of these agents in clinical practice is restricted by various factors, including the development of acquired resistance due to the presence of compensatory pathways. BETis can completely disrupt the HR pathway by repressing the expression of BRCA1 and could be aimed at generation combination regimes to overcome PARPi resistance and enhance PARPi efficacy.

Synthesis of High Molecular Weight Stereo-Di-Block Copolymers Driven by a Co-Initiator Free Catalyst.

Stereo-diblock copolymers of high molecular weight polylactide (PLA) were synthetized by the one pot-sequential addition method assisted by a heteroscorpionate catalyst without the need of a co-initiator. The alkyl zinc organometallic heteroscorpionate derivative (Zn(Et)(κ-bpzteH)] (bpzteH = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-para-tolylethoxide) proved to assist in the mechanism of reaction following a coordination-insertion process. Kinetic studies along with the linear correlation between monomer and number average molecular weight (M) conversion, and the narrow polydispersities supported the truly living polymerization character of the initiator, whereas matrix-assisted laser desorption/Ionization-time of flight (MALDI-TOF) studies showed a very low order of transesterification.

Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(-lactide)s.

The direct reaction of the highly sterically demanding acetamidinate-based NNN'-scorpionate protioligand Hphbpamd [Hphbpamd = ,'-di-p-tolylbis(3,5-di-tertbutylpyrazole-1-yl)acetamidine] with one equiv. of ZnMe proceeds in high yield to the mononuclear alkyl zinc complex [ZnMe(-phbpamd)] (). Alternatively, the treatment of the corresponding lithium precursor [Li(phbpamd)(THF)] with ZnCl yielded the halide complex [ZnCl(-phbptamd)] ().

Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts.

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened.

Controlled Delivery of BET-PROTACs: In Vitro Evaluation of MZ1-Loaded Polymeric Antibody Conjugated Nanoparticles in Breast Cancer.

Bromo and extraterminal domain (BET) inhibitors-PROteolysis TArgeting Chimera (BETi-PROTAC) is a new family of compounds that induce proteasomal degradation through the ubiquitination of the tagged to BET inhibitors Bromodomain proteins, BRD2 and BRD. The encapsulation and controlled release of BET-PROTACs through their vectorization with antibodies, like trastuzumab, could facilitate their pharmacokinetic and efficacy profile. Antibody conjugated nanoparticles (ACNPs) using PROTACs have not been designed and evaluated.

NNC-Scorpionate Zirconium-Based Bicomponent Systems for the Efficient CO Fixation into a Variety of Cyclic Carbonates.

Two new derivatives of the bis(3,5-dimethylpyrazol-1-yl)methane modified by introduction of organosilyl groups on the central carbon atom, one of which bearing a chiral fragment, have been easily prepared. We verified the potential utility of these compounds through the reaction with [Zr(NMe)] for the preparation of novel zirconium complexes in which an ancillary bis(pyrazol-1-yl)methanide acts as a robust monoanionic tridentate scorpionate in a -NNC chelating mode, forming strained four-membered heterometallacycles. These -NNC-scorpionate zirconium amides were investigated as catalysts in combination with tetra--butylammonium bromide as cocatalyst for CO fixation into five-membered cyclic carbonate products.

PEI-coated PLA nanoparticles to enhance the antimicrobial activity of carvacrol.

Carvacrol (CAR) is a natural bioactive compound with antioxidant and antimicrobial activity that is present in essential oils. The application of CAR in food preservation is hampered by its high volatility, low solubility in water, and susceptibility to light, heat and oxygen degradation. Polylactide (PLA) is an FDA-approved polymer derived from renewable resources.