Antibacterial activity of withanolides, labdane glucosides, flavonoids and other constituents from two populations of Physalis patula.

Two populations of Physalis patula Miller collected in different localities (Querétaro and Teotihuacán) of Central México were analyzed. Eight new compounds including three withanolides, physapatolides A-C (1-3), two labdanes, 12-epi-physacoztomatin (10) and physapatulone (12), besides three 12-O-glucosyl labdanes, patulosides A-C (13-15), were isolated from these collections. A series of known withanolides, flavonoids, labdanes, sucrose esters, and sterols were also isolated.

Stereoelectronic interactions are too weak to explain the molecular conformation in solid state of -2--butyl-5-(-butylsulfonyl)-1,3-dioxane.

-2--Butyl-5-(-butylsulfonyl)-1,3-dioxane (-1) exhibits a high degree of eclipsing in the H-C5-S-C segment in the solid state, the origin of which remains unexplained. The eclipsed conformation that corresponds to an energetic minimum in the solid state practically corresponds to a rotational transition state in solution, which allows an approach to understand transitions states. The difference in the enthalpy of sublimation Δ between -1 and the more stable -1 is 8.

Synthesis of Functionalized Tetrasubstituted Allenes by the Addition of Bis(trimethylsilyl)ketene Acetals to Ynones Catalyzed by Gold(I).

We have developed a straightforward and rapid methodology for the synthesis of tetrasubstituted allenes bearing carboxylic acids in the 1,3-position through the gold(I)-catalyzed nucleophilic addition of bis(trimethylsilyl)ketene acetals to ynones. The reaction was evaluated with several substrates, and 21 allenes were obtained in moderate to good yields. Using DFT calculations, we studied the mechanism of the reaction, which suggested a nucleophilic 1,4-addition pathway.

Well-defined Cu(I) complexes based on [N,P]-pyrrole ligands catalyzed a highly endoselective 1,3-dipolar cycloaddition.

We herein report the synthesis and catalytic application of a new family of dinuclear Cu(I) complexes based on [N,P]-pyrrole ligands. The Cu(I) complexes (4a-d) were obtained in good yields and their catalytic properties were evaluated in the1,3-dipolar cycloaddition of azomethine ylides and electron-deficient alkenes. The air-stable complexes 4a-d exhibited high endo-diasteroselectivity to obtain substituted pyrrolidines, and the catalytic system showed excellent reactivity and wide substitution tolerance.

Design of Promising Uranyl(VI) Complexes Thin Films with Potential Applications in Molecular Electronics.

In this work, it is proposed the development of organic semiconductors (OS) based on uranyl(VI) complexes. The above by means of the synthesis and the characterization of the complexes by Infrared spectroscopy, Nuclear magnetic resonance spectroscopy, mass spectrometry, and X-ray diffraction. Films of these complexes were deposited and subsequently, topographic and structural characterization was carried out by Scanning Electron Microscopy, X-ray diffraction, and Atomic Force Microscopy.

First Gallium and Indium Crystal Structures of Curcuminoid Homoleptic Complexes: All-Different Ligand Stereochemistry and Cytotoxic Potential.

The crystal structure determination of metal complexes of curcuminoids is a relevant topic to assess their unequivocal molecular structure. We report herein the first two X-ray crystal structures of homoleptic metal complexes of a curcuminoid, namely Dimethoxycurcumin (DiMeOC), with gallium and indium. Such successful achievement can be attributed to the suppression of interactions from the phenolic groups, which favor an appropriate molecular setup, rendering Dimethoxycurcumin gallium ((DiMeOC)-Ga) and Dimethoxycurcumin indium ((DiMeOC)-In) crystals.

The Homoleptic Curcumin-Copper Single Crystal (ML): A Long Awaited Breakthrough in the Field of Curcumin Metal Complexes.

The first single crystal structure of the homoleptic copper (II) ML complex (M=Cu (II), L = curcumin) was obtained and its structure was elucidated by X-ray diffraction showing a square planar geometry, also confirmed by EPR. The supramolecular arrangement is supported by C-H···O interactions and the solvent (MeOH) plays an important role in stabilizing the crystal packing Crystallinity was additionally assessed by XRD patterns. The log P value of the complex (2.

Unreported ent-rosane diterpenes from Croton niveus Jacq. (Euphorbiaceae). Cytotoxic activity and docking studies.

From the bioactive extract of the euphorbiaceous Croton niveus Jacq., three previously unreported ent-rosane diterpenes have been isolated and characterized by conventional methods, in addition to the known compounds lupeol, cajucarinolide and some phytosterols. Two of the ent-rosane diterpenes displayed activity against HCT-15 and PC-3 cancer cell lines, and the results of docking calculations of these compounds with NF-κB and STAT3 receptors agreed with the proposed mode of action of diterpenes against PC-3 cells.

Three new coordination geometries of homoleptic Zn complexes of curcuminoids and their high antiproliferative potential.

To our previously reported first crystal structure of a homoleptic zinc curcuminoid complex with square pyramidal geometry, we add herein three new geometries of homoleptic type complexes octahedral, trigonal-pyramidal, and trigonal-bipyramidal. Octahedral geometry was observed in the new pseudo-polymorph of the DAC-Zn complex resulting from crystallization in DMF, while square-pyramidal geometry was obtained in DMSO. Improving crystallinity involved suppressing the phenolic interactions by etherification and esterification.

Homoleptic Complexes of Heterocyclic Curcuminoids with Mg(II) and Cu(II): First Conformationally Heteroleptic Case, Crystal Structures, and Biological Properties.

We report herein the synthesis and characterization of three heterocyclic curcuminoid ligands and their homoleptic metal complexes with magnesium and copper. Thus, N-methyl-2-pyrrolecarboxaldehyde, Furan-2-carboxaldehyde, and 2-Thiophenecarboxaldehyde were condensed with 2,4-pentanedione-boron trioxide complex. The first N-methyl-2-pyrrole curcuminoid and its Mg(II) complex are reported.

2-Amino-4-ferrocenyl-thia-zole.

The title compound, [Fe(CH)(CHNS)], was synthesized by the direct reaction of acetyl-ferrocene, thio-urea and resublimed iodine. The structure shows one mol-ecule in the asymmetric unit. The amino-thia-zole ring makes an angle of 14.

Diastereomeric Separation of Chiral -Tricarbonyl(iminopyridine) Rhenium(I) Complexes and Their Cytotoxicity Studies: Approach toward an Action Mechanism against Glioblastoma.

A series of new (tricarbonyl)rhenium(I) complexes were synthesized using chiral bidentate ligands (+)/(-)-iminopyridines (L/L). The reaction yielded a mixture of mononuclear Re(I) diastereoisomers, formulated as -[Br(CO)ReL]. Each single diastereoisomer was isolated and fully characterized.

9-Trifluoromethylxanthenediols: Synthesis and Supramolecular Motifs.

The synthesis of four derivatives and the single-crystal X-ray structures of six 9-trifluoromethylxanthenediols (TFXdiols) - are analyzed in this work. These compounds were obtained through superacid-catalyzed condensation of dihydroxybenzenes with 1,1,1-trifluoroacetone or 2,2,2-trifluoroacetophenone. The title molecules have a convex molecular structure due to their three fused rings of the xanthene moiety.

Tailoring the cavities of hydrogen-bonded amphidynamic crystals using weak contacts: towards faster molecular machines.

This work describes the use of C-H⋯F-C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors . The crystal structures of these rotors, determined by synchrotron radiation experiments at different temperatures, show the presence of such C-H⋯F-C contacts between extended carbazole stators featuring fluorinated phenyl rings and the 1,4-diazabicyclo[2.2.

Non-Cytotoxic Dibenzyl and Difluoroborate Curcuminoid Fluorophores Allow Visualization of Nucleus or Cytoplasm in Bioimaging.

Curcumin, the most important secondary metabolite isolated from , is known for its numerous purported therapeutic properties and as a natural dye. Herein, based on curcumin's intrinsic fluorescence, a search for improved curcumin-based fluorophores was conducted. Within the set of semi-synthetic curcumin derivatives i.

Hydrogen-Bonded Crystalline Molecular Machines with Ultrafast Rotation and Displacive Phase Transitions.

Two new crystalline rotors 1 and 2 assembled through N-H⋅⋅⋅N hydrogen bonds by using halogenated carbazole as stators and 1,4-diaza[2.2.2]bicyclooctane (DABCO) as the rotator, are described.

Triggering the dynamics of a carbazole-p-[phenylene-diethynyl]-xylene rotor through a mechanically induced phase transition.

A new rotor exhibits rich solvatomorphism behavior with eight X-ray structures obtained. A heterogeneous solid obtained by mechanical stress exhibited a dominant isotropic H line shape at high temperatures. The motion occurs only in the amorphous component of this solid, with an E of 7.

Further galphimines from a new population of Galphimia glauca.

Both DNA barcoding and phylogenetic data of the studied botanical material suggested the existence a new population of Galphimia glauca. Their leaves afforded three new nor-3,4-seco-friedelanes named galphimines M-O, together with known galphimines D, E, G, and I. Galphimines M and N possess bicyclic orthoacetates which are the first examples of orthoesters found in the Malpighiaceae family, while galphimine O has a 27,20-δ-lactone moiety.

Structural Reassignment of -(3',3,6,7,3a',6')-3,8-Dihydrodiligustilide and the Activity of Diligustilide and 3,8-Dihydro- and 3,8,7',7a'-Tetrahydrodiligustilides as Progestins.

Several phthalides were semisynthesized, including a 3,8-dihydrodiligustilide with progesterone-like activity, previously isolated from , the structure of which was earlier assigned to a semisynthetic product with nonidentical spectroscopic constants. The structure of this natural phthalide was reassigned with a proposal of its absolute configuration. Phthalides acted as progestins in cell viability assays, immunofluorescence microscopy, and docking analysis.

Labdanes, Withanolides, and Other Constituents from .

Chemical investigation of the aerial parts (except fruits and calixes) of var. led to the isolation of a series of new labdane-type diterpenoids, including the closely related compounds -, the labdane glucosides and , a mixture of the epimeric alcohols and , and one labdanetriol, isolated as its tri--acetyl derivative . In addition, three new withanolides (-) and six known compounds were isolated.

Origin of the isotropic motion in crystalline molecular rotors with carbazole stators.

Herein we report two crystalline molecular rotors and that show extremely narrow signals in deuterium solid-state NMR spectroscopy. Although this line shape is typically associated with fast-moving molecular components, our VT H NMR experiments, along with X-ray diffraction analyses and periodic DFT computations show that this spectroscopic feature can also be originated from low-frequency intramolecular rotations of the central phenylene with a cone angle of 54.7° that is attained by the cooperative motion of the entire structure that distorts the molecular axis to rotation.

A New Family of Homoleptic Copper Complexes of Curcuminoids: Synthesis, Characterization and Biological Properties.

We report herein the synthesis and crystal structures of five new homoleptic copper complexes of curcuminoids. The scarcity of reports of homoleptic complex structures of curcuminoids is attributed to the lack of crystallinity of such derivatives, and therefore, their characterization by single crystal X-ray diffraction is rare. The ligand design suppressing the phenolic interaction by esterification or etherification has afforded a significant increase in the number of known crystal structures of homoleptic metal complexes of curcuminoids revealing more favorable crystallinity.

Multifunctional Fischer Aminocarbene Complexes as Hole or Electron Transporting Layers in Organic Solar Cells.

A new series of Fischer carbenes have been synthetized and examined as hole-transporting or electron-transporting layers (HTLs or ETLs) in the fabrication of organic solar cells (OSCs). The synthesis of three Fischer aminocarbene complexes with the general formula [Cr(CO)₅{C(NHCH₂)Ar}] (Ar = 2-pyridyl (), 3-pyridyl () and 4-pyridyl ()) is reported. The molecular structure of complex has been confirmed by X-ray analysis.