Physicochemical properties and mechanism of action of a new copper(ii) pyrazine-based complex with high anticancer activity and selectivity towards cancer cells.

Two compounds, benzyl-2-(amino(pyrazin-2-yl)methylene)-1-methylhydrazine-1-carbodithioate (L) and its copper(ii) complex Cu(L) were synthesized and studied in terms of their physicochemical properties, including single crystal, spectroscopic and magnetic properties; simulations, including DFT calculations and pharmacokinetic profile analysis; and biological activity. The Cu(L) compound was found to exhibit good anticancer activity against A375, PANC-1, MKN-74, T-47D, HeLa, and NCI-H1563 cells, with the IC value against the HeLa cell line reaching 17.50 μM, significantly surpassing the activity of the organic ligand.

Helical polyamines.

Polymer microstructures rely on tacticity, yet exploration in polyamines has focused predominantly on atactic polymers. We introduce a method to synthesize a diverse library of and -cyanobenzenesulfonyl-activated-methyl aziridines using , , and racemic alaninol. Living anionic ring-opening polymerization of racemic sulfonyl aziridines yields soluble polymers, while enantiomerically-pure sulfonyl aziridines follow a dispersion polymerization with complete monomer conversion giving access to stereoblock copolymers.

Decarboxylative photoinduced ligand-to-metal charge transfer reaction: synthesis of 2-substituted chroman-4-ones.

In this manuscript, a photoinduced ligand-to-metal charge transfer (LMCT) approach, employing transition-metal-based photocatalysts, for the efficient alkylation of electron-poor olefin is described. The developed redox-neutral process benefits from mild reaction conditions and involves a wide range of chromone-3-carboxylic acids as well as nucleophiles amenable to selective C-H functionalization leading to the formation of 2-substituted chroman-4-one compounds with potential biological activity.

Antimicrobial and Biodegradable 3D Printed Scaffolds for Orthopedic Infections.

In bone tissue engineering, the performance of scaffolds underpins the success of the healing of bone. Microbial infection is the most challenging issue for orthopedists. The application of scaffolds for healing bone defects is prone to microbial infection.

Pentaenolate activation in the organocatalytic allylic alkylation of indene-2-carbaldehydes.

In this manuscript, the application of pentaenolate intermediates in the allylic alkylation of indene-2-carbaldehydes with Morita-Baylis-Hillman (MBH) carbonates is described. The reaction has been carried out in a highly enantio- and diastereoselective manner due to the use of a chiral tertiary amine as a nucleophilic catalyst. The developed reactivity constitutes the first application of organocatalytic pentaenolate activation in asymmetric synthesis, expanding the arsenal of catalytic methods.

Exhaustive Baeyer-Villiger oxidation: a tailor-made post-polymerization modification to access challenging poly(vinyl acetate) copolymers.

The discovery of exhaustive (nearly quantitative) post-polymerization modifications (PPM) relies heavily on the efficiency of their corresponding small-molecule protocols. However, the direct translation of existing small-molecule protocols into PPM methods has never been guaranteed due to the intrinsic differences between small-molecule substrates and polymers. Herein, we introduce the direct optimization on polymers (DOP) as a complementary approach to developing exhaustive PPM reactions.

A library of new bifunctional alkenes obtained by a highly regiodivergent silylation of 1,5-hexadiene.

An efficient methodology for the synthesis of two groups of silicon-containing alkenes is reported. It includes a highly regioselective functionalization of 1,5-hexadiene through hydrosilylation and dehydrogenative silylation with organofunctional silanes and siloxanes. The established conditions enable selective monofunctionalization of 1,5-hexadiene regardless of the organosilicon modifier used as well as the type of functional group bonded to the silicon-based compound.

Visible-light synthesis of 4-substituted-chroman-2-ones and 2-substituted-chroman-4-ones doubly decarboxylative Giese reaction.

Doubly decarboxylative, photoredox synthesis of 4-substituted-chroman-2-ones and 2-substituted-chroman-4-ones is described. The reaction involves two independent decarboxylation processes: the first one initiating the cycle and the second completing the process. Visible light, photoredox catalyst, base, anhydrous solvent and inert atmosphere constitute the key parameters for the success of the developed transformation.

RNA-inspired intramolecular transesterification accelerates the hydrolysis of polyethylene-like polyphosphoesters.

To synthesize new (bio)degradable alternatives to commodity polymers, adapting natural motives can be a promising approach. We present the synthesis and characterization of degradable polyethylene (PE)-like polyphosphoesters, which exhibit increased degradation rates due to an intra-molecular transesterification similar to RNA. An α,ω-diene monomer was synthesized in three steps starting from readily available compounds.

Efficient access to 3'--phosphoramidite derivatives of tRNA related -threonylcarbamoyladenosine (tA) and 2-methylthio- -threonylcarbamoyladenosine (mstA).

An efficient method of ureido linkage formation during epimerization-free one-pot synthesis of protected hypermodified -threonylcarbamoyladenosine (tA) and its 2-SMe analog (mstA) was developed. The method is based on a TfO-mediated direct conversion of the -Boc-protecting group of -Boc-threonine into the isocyanate derivative, followed by reaction with the -amine function of the sugar protected nucleoside (yield 86-94%). Starting from 2',3',5'-tri--acetyl protected adenosine or 2-methylthioadenosine, the corresponding 3'--phosphoramidite monomers were obtained in 48% and 42% overall yield (5 step synthesis).

Novel entry to the synthesis of ()- and ()-5-methoxycarbonylhydroxymethyluridines - a diastereomeric pair of wobble tRNA nucleosides.

Two novel methods for the preparation of the virtually equimolar mixtures of ()- and ()-diastereomers of 5-methoxycarbonylhydroxymethyluridine (mchmU) have been developed. The first method involved α-hydroxylation of a 5-malonate ester derivative of uridine (5) with SeO, followed by transformation to ()- and ()-5-carboxymethyluridines (cmU, 8) and, finally, into the corresponding methyl esters. In the second approach, ()- and ()-mchm-uridines were obtained starting from 5-formyluridine derivative (9) by hydrolysis of the imidate salt (11) prepared in the acid catalyzed reaction of 5-cyanohydrin-containing uridine (10b) with methyl alcohol.

2-Substituted 1,4-Naphthoquinones in [6 + 4]-Cycloaddition with 8,8-Dicyanoheptafulvene.

This study demonstrates that classical lowest unoccupied molecular orbital reactivity of 2-substituted 1,4-naphthoquinones is possible to be reversed by deprotonation and application of the resulting dienolate as a 4π component in the higher-order [6 + 4]-cycloaddition proceeding in a completely pericyclic manner. 8,8-Dicyanoheptafulvene was shown to be an efficient 6π component in the developed reaction opening the access to functionalized cycloadducts in a diastereoselective manner by employing organocatalytic activation. Attempts to introduce enantioselective version of the developed higher-order cycloaddition were also undertaken.

Effect of fluorination of naphthalene diimide-benzothiadiazole copolymers on ambipolar behavior in field-effect transistors.

Two naphthalene diimide (NDI)-benzothiadiazole (BT) based conjugated polymers with high molecular weight, P1 and P2, were synthesized by introducing F atoms to modulate the electron-donating ability of the BT moiety. 3-Decyl-pentadecyl branched alkyl side chains were employed and expected to improve the molecular organization and device performance. Both polymers have excellent solubility in common organic solvents.