New Hydroxylactones and Chloro-Hydroxylactones Obtained by Biotransformation of Bicyclic Halolactones and Their Antibacterial Activity.

The aim of this study was to obtain new halolactones with a gem-dimethyl group in the cyclohexane ring (at the C-3 or C-5 carbon) and a methyl group in the lactone ring and then subject them to biotransformations using filamentous fungi. Halolactones in the form of mixtures of two diasteroisomers were subjected to screening biotransformations, which showed that only compounds with a gem-dimethyl group located at the C-5 carbon were transformed. Strains from the genus carried out hydrolytic dehalogenation, while strains from the genus carried out hydroxylation of the C-7 carbon.

Iminopyrrole-Based Self-Assembly: A Route to Intrinsically Flexible Molecular Links and Knots.

The use of 2,5-diformylpyrrole in self-assembly reactions with diamines and Zn(II)/Cd(II) salts allowed the preparation of [2]catenane, trefoil knot, and Borromean rings. The intrinsically dynamic nature of the diiminopyrrole motif rendered all of the formed assemblies intramolecularly flexible. The presence of diiminopyrrole revealed new coordination motifs and influenced the host-guest chemistry of the systems, as illustrated by hexafluorophosphate encapsulation by Borromean rings.

21-Carba-23-selenaporphyrinoid Dyads-An Azepine Unit as a Merging Motif.

The oxidation of 10,15-diaryl-21-carba-23-selenaporphyrinoids resulted in the creation of dyads. The dimerization process follows a [5+2] cycloaddition path with the formation of an azepine unit. The arrays display two direct bonds between the peripheral carbocyclic carbon atoms of one carbaselenaporphyrinic subunit and the central carbon and nitrogen atoms of the second subunit.

Bromine versus chlorine substituent in breathing crystals of a copper(I) coordination compound with a triazolamine Schiff base.

It is known that N-[4-(chlorobenzylidene)-4H-1,2,4-triazol-4-amine in reaction with copper(I) perchlorate(VII) forms metastable breathing crystals built up of X-shaped binuclear units containing copper(I) ions in a trigonal coordination sphere. Using trifluoromethanesulfonate instead of perchlorate(VII) affects the self-assembly of the X-shaped units and the breathing function of the resulting crystals. The latter are not breathing crystals.

The Intracavity Extension of 28-Hetero-2,7-naphthiporphyrins in Reactions with Alkylamines.

The 28-hetero-2,7-naphthiporphyrins reacted with triethylamine and diethylamine to form nonaromatic intracavity-extended macrocycles incorporating naphthodihydro-2-pyran, naphthotetrahydropyridine, and naphthopyrrolotetrahydro-1-azepine moieties. The new macrocycles were characterized in solution by means of NMR and UV-vis spectroscopy and in the solid state by XRD.

POSSaxanes: active-template synthesis of organic-inorganic rotaxanes incorporating cubic silsesquioxane stoppers.

The CuAAC active-template approach was exploited to construct rotaxanes incorporating cage-like silsesquioxane stoppers, namely, POSSaxanes. The compounds were characterized in the solution and solid state, providing the unprecedented molecular structures of POSS-incorporating rotaxanes.

Heterobimetallic 21,23-dimetallaporphyrin: activation of metal-metal interactions within the porphyrinoid macrocycle.

Two core-modified porphyrins containing metal atoms, namely platinum(II) or platinum(IV) and rhodium(III), in place of two NH units, have been obtained by a post-synthetic modification of the 21,23-ditelluraporphyrin. The products of the tellurium-to-metal exchange, 21-platina-23-rhodaporphyrins, incorporate rhodacyclopentadiene and platinacyclopentadiene units with the metal atoms facing each other. The two molecules exhibit different degrees of metal-metal interaction depending on the oxidation state of platinum, with the NBO bond order being 0.

Chalcone-Derived Lactones: Synthesis, Whole-Cell Biotransformation, and Evaluation of Their Antibacterial and Antifungal Activity.

Four compounds with lactone moiety were synthesized from chalcone in three- or four-step synthesis. γ-Bromo-δ-lactone was the only product of bromolactonization of acid whereas bromolactonization of ester , apart from lactone also afforded its isomer and two diastereoisomeric δ-hydroxy-γ-lactones and . Lactone was also obtained in 88% yield as a product of simultaneous dehalogenation and translactonization of γ-bromo-δ-lactone by AM 359.

Progressive Structural Complexity in Ferroelectric 1,2,4-Triazolium Hexabromoantimonate(III): Interplay of "Order-Disorder" and "Displacive" Contributions to the Structural Phase Transitions.

Halobismuthates(III) and haloantimonates(III) with the RMX chemical composition create a new and broadly unexplored class of ferroelectric compounds. In this paper, we report the haloantimonate(III) ferroelectric comprising an aromatic (1,2,4-triazolium) cation, i.e.

Metalation of Tellurophene: Reactivity of 21,23-Ditelluraporphodimethene toward Palladium(II), Platinum(II), and Rhodium(I).

Ditelluraporphodimethene, a nonaromatic porphyrinoid containing two tellurophene rings, reacted with palladium(II), platinum(II), and rhodium(I) following two different paths. Palladium(II) formed bonds to two tellurium donors of the macrocycle, yielding a side-on coordination compound, with a square planar (TeCl) metal ion environment. An alternative reaction path has been observed for ditelluraporphodimethene with platinum(II) or rhodium(I) in high boiling solvents.

Plenates: Anion-Dependent Self-Assembly of the Pyrrole Cage Encapsulating Silver(I) Clusters.

The self-assembly of 2,5-diformylpyrrole, tris(2-aminoethyl)amine, and silver(I) yielded, depending on the size and basicity of the anion, new cascade complexes or plenates, that is, cryptates incorporating Ag clusters. The nature of the product was counterion-dependent, and its formation was either driven by cascade anion binding or by argentophilic interactions stabilizing the cluster within the cavity. The reaction of plenates with tetrabutylammonium halides resulted in the protonation-coupled replacement of the Ag with anion(s), yielding cascade cryptates.

Crownphyrins: Metal-Mediated Transformations of the Porphyrin-Crown Ether Hybrids.

Crownphyrins are hybrid macrocycles combining structural features of porphyrin and crown ethers. The molecular architecture renders them an intriguing class of hosts capable of binding neutral, and ionic guests. The presence of dynamic covalent imine linkages connecting the dipyrrin segment with the ether chain enables unusual coordination behavior of crownphyrins, as demonstrated by the formation of two classes of strikingly different complexes.

Two Rhodium(III) Ions Confined in a [18]Porphyrin Frame: 5,10,15,20-Tetraaryl-21,23-dirhodaporphyrin.

Invited for the cover of this issue is the group of Ewa Pacholska-Dudziak at the University of Wroclaw. The image depicts two rhodium atoms being fixed into the skeleton of 21,23-dirhodaporphyrin in place of two core nitrogen donors. Read the full text of the article at 10.

Two Rhodium(III) Ions Confined in a [18]Porphyrin Frame: 5,10,15,20-Tetraaryl-21,23-Dirhodaporphyrin.

Tetraaryl-21,23-dirhodaporphyrin and a series of related monorhodaporphyrins have been obtained by tellurium-to-rhodium exchange in a reaction of tetraaryl-21,23-ditelluraporphyrin with [RhCl(CO) ] . These organometallic metallaporphyrins contain rhodium(III) centers embedded in rhodacyclopentadiene rings, incorporated within the porphyrin frames. The skeletons of 21,23-dirhodaporphyrin and 21-rhoda-23-telluraporphyrin are strongly deformed in-plane from the rectangular shape typical for porphyrins, due to rhodium(III) coordination preferences, the large size of the two core atoms, and the porphyrin skeleton constrains.

Kinetic versus Thermodynamic Control Over Multiple Conformations of Di-2,7-naphthihexaphyrin(1.1.1.1.1.1).

Di-2,7-naphthihexaphyrin(1.1.1.

New anticandidal Cu(i) complexes with neocuproine and ketoconazole derived diphenyl(aminomethyl)phosphane: luminescence properties for detection in fungal cells.

The search for new antifungals is very important because the large genetic variation of pathogenic organisms has resulted in the development of increasingly effective defense mechanisms by microorganisms. Metal complexes as potential drugs are nowadays gaining interest, because they are characterized by accessible redox states of metal centers and a plethora of easily modifiable geometries. In this work we present two new copper(i) iodide or thiocyanide complexes with 2,9-dimethyl-1,10-phenanthroline (dmp) and a diphenylphosphane derivative of ketoconazole (KeP), where a ketoconazole acetyl group is replaced by the -CHPPh unit, [CuI(dmp)KeP] (1-KeP) and [CuNCS(dmp)KeP] (2-KeP) - their synthesis and structural characteristics.

Chemistry inside a Porphyrin Skeleton: Platinacyclopentadiene from Tellurophene.

Platinum(II) binds to 21,23-ditelluraporphyrin forming a side-on complex, which can be easily transformed into an aromatic metallaporphyrin, that is, 21-platina-23-telluraporphyrin, with a platinacyclopentadiene unit built in the porphyrin skeleton in place of one pyrrole ring. The central platinum(II) ion with a CCNTe square-planar coordination sphere can be oxidized to platinum(IV) by chlorine, bromine, methyl iodide or allyl chloride to yield octahedral complexes. All platinatelluraporphyrins show dynamic behavior involving the platinum ion coordination sphere fluxionality and the porphyrin skeleton deformation, both in-plane and out-of-plane, as demonstrated by H NMR spectroscopy.

Conformation-Dependent Response to the Protonation of Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): A Route to Pseudorotaxane-Like Structures.

Diphenanthrioctaphyrin(1.1.1.

Mixed-Generation PAMAM G3-G0 Megamer as a Drug Delivery System for Nimesulide: Antitumor Activity of the Conjugate Against Human Squamous Carcinoma and Glioblastoma Cells.

Polyhydroxylated dendrimer was synthesized from poly(amidoamine) (PAMAM) dendrimer generation 3 by addition of glycidol (). megamer was further modified by binding PAMAM G0 dendrimers by activation of with -nitrophenylchloroformate, followed by the addition of excess PAMAM G0 and purification using dialysis. The maximum G0 binding capacity of was 12 in the case when G0 was equipped with two covalently attached nimesulide equivalents.

Oxygenation of Phenanthriporphyrin and Copper(III) Phenanthriporphyrin: An Efficient Route to Phenanthribilinones.

Photooxidation of copper(III) 5,6-dimethoxyphenathriporphyrin and copper(III) 5,6-dioxophenanthriporphyrin, which contain phenanthrene or dioxophenathrene moieties built into the macrocyclic frameworks, resulted in the regioselective cleavage that afforded organometallic copper(III) complexes of open-chain phenanthribilinone-type acyclic ligands terminated by carbonyl groups. The copper(III) coordinates two carbon atoms of phenantherene (dioxophenanthrene) and two nitrogen atoms of pyrrole and pyrrolone units, preserving the donor sets of the paternal complexes. The primary dioxygen attack is located at the carbon atom adjacent to the phenanthrene moiety.

28-Hetero-2,7-Naphthiporphyrins: Horizontal Expansion of the -Benziporphyrin Macrocycle.

Replacement of the -phenylene moiety of -benziporphyrins with the 2,7-naphthalenyl subunit yielded 28-hetero-2,7-naphthiporphyrins-macrocycles that can be considered as expanded carbaporphyrinoids. This group retains some features of parent -benziporphyrins, but due to larger size and different shape of the macrocyclic cavity, their coordination properties are different. Upon reduction and conformational rearrangement the 28-thia- and 28-selena-2,7-naphthiporphyrin form organophosphorus(V) complexes.

Light-stable polypyridine silver(i) complexes of 1,3,5-triaza-7-phosphaadamantane (PTA) and 1,3,5-triaza-7-phosphaadamantane-7-sulfide (PTA[double bond, length as m-dash]S): significant antiproliferative activity of representative examples in aqueous media.

A series of novel silver(i) 2,2':6',2''-terpyridine (tpy), 4'-(4-methylphenyl)-2,2':6':2''-terpyridine (tpy-Ph-Me) and 1,10-phenanthroline-5,6-dione (dione) derivatives containing PTA (1,3,5-triaza-7-phosphaadamantane) or 1,3,5-triaza-7-phosphaadamantane-7-sulfide (PTA[double bond, length as m-dash]S) have been synthesized and fully characterized. Two types of complexes have been obtained, monocationic [Ag(tpy)(PTA)](NO) (1), [Ag(tpy-Ph-Me)(PTA)](NO) (2), [Ag(dione)(PTA[double bond, length as m-dash]S)](BF) (4) and [Ag(dione)](PF) (5) and neutral [Ag(dione)(PTA[double bond, length as m-dash]S)(NO)] (3). The solid-state structures of four complexes have been determined by single-crystal X-ray diffraction.

New -Halo--lactones and -Hydroxy--lactones with Strong Cytotoxic Activity.

This paper presents the synthesis of γ -halo- δ -lactones, δ -iodo- γ -lactones and δ -hydroxy- γ -lactones from readily available organic substrates such as -crotonaldehyde and aryl bromides. Crystal structure analysis was carried out for lactones that were obtained in crystalline form. All halo- δ -lactones and δ -hydroxy- γ -lactones were highly cytotoxic against gastric cancer AGS cells with I C 50 values in the range of 0.

Shaping a Porphyrinoid Frame by Heteroatoms Extrusion: Formation of an Expanded [22]Triphyrin(6.6.0).

An aromatic expanded triphyrin, [22]triphyrin(6.6.0) 2, containing a pyrrole unit, a bipyrrole moiety, and annulene links, was obtained from a tellurium-containing precursor meso-tetraaryl-26,28-ditellurasapphyrin 1.

Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): Conformational Switching Controls the Stereochemical Dynamics of the Topologically Chiral System.

The analogue of octaphyrin(1.1.1.