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Twelve selenourea having fluorinated fragments were synthesized and fully characterized and their fluorine content influence studied by 77Se NMR.

The tropical tree Calophyllum brasiliense Cambess. (Clusiaceae) grows in rain forests from Brazil to Mexico. Its leaves, as well as those of other Calophyllum species, are rich sources of chromanone acids, such as apetalic acid, isoapetalic acid, and their derivatives. Apetalic acid has shown significant antimycobacterial activity. The biological activity of apetalic acid has been related to the configuration of three asymmetric centers and the stereochemistry of the molecule; however, the C-19 configuration in the acidic side chain has not been fully resolved. For this reason, the unequivocal determination of the absolute configuration by means of X-ray crystallography in a sample of unique homogeneous apetalic acid stereoisomer was the most important point to start this study. Chiral amides were prepared using the carboxyl group. We determined the C-19 stereochemistry of apetalic acid and its specific chiral derivatives using NMR, X-ray diffraction, and molecular mechanics. Finally, we observed that steric hindrance in the side chain of apetalic acid leads to restriction of rotation around the pivotal linkage C-10–C-19, establishing chiral centers at C2(R), C3(S), and C19(R). We were able to separate the derivatives of these two high-rotatory-barrier conformers of apetalic acid by forming diastereoisomeric amides with phenylglycine methyl ester having a chiral center at C-2′. Our results confirmed the existence of atropisomerism in the apetalic acid molecule.

The solvatomorphs of [Pd(1,10-phen)(2,3,5,6-S-C6F4H)2] 1 (1,10-phen = 1,10-phenanthroline), i.e., 1·S (S = C6H62, C6H6Cl 3 and C6H6Br 4) and [Pd(1,10-phen)(2,3,4,5,6-S-C6F5)2]·C6H6Br 5 were studied to shed further light on the solvatomorphism phenomena.

A series of Rh(i) complexes with fluorinated NHC ligands were prepared and used as efficient catalysts in the arylation of aldehydes.

The synthesis of four pentacoordinated organotin(IV) complexes prepared in a one-pot reaction from 2-hydroxy-1-naphthaldehyde, 2-amino-3-hydroxypyridine and organotin oxides is reported. The complexes were characterized by UV-Vis, IR, MS, 1H, 13C and 119Sn NMR techniques. The compound based on 2,2-diphenyl-6-aza-1,3-dioxa-2-stannanaphtho[1,2-h]pyrido[3,2-d]cyclononene revealed the formation of a monomeric complex with a distorted five-coordinated molecular geometry intermediate between the trigonal bipyramidal and square pyramidal. In order to find possible applications in photovoltaic devices, hybrid films of organotin(IV) complexes embedded in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with graphene were deposited. The topographic and mechanical properties were examined. The film with the complex integrated into the cyclohexyl substituent has high plastic deformation, with a maximum stress of 1.69 × 107 Pa and a Knoop hardness of 0.061. The lowest values of 1.85 eV for the onset gap and 3.53 eV for the energy gap were obtained for the heterostructure having the complex with the phenyl substituent. Bulk heterojunction devices were fabricated; these devices showed ohmic behavior at low voltages and a space-charge-limited current (SCLC) conduction mechanism at higher voltages. A value of 0.02 A was found for the maximum carried current. The SCLC mechanism suggests hole mobility values of between 2.62 × 10−2 and 3.63 cm2/V.s and concentrations of thermally excited holes between 2.96 × 1018 and 4.38 × 1018 m−3.

The natural compound 25,26,27-tris

A multicomponent reaction was used as a synthetic strategy to prepare organotin (IV) complexes, 2-amino-3-hydroxypyridine, saliciladehydes 5-R-substituted (H, CH3, OCH3, C(CH)3, F, Cl, Br, I, NO2), and dibutyltin(IV) oxide were used as starting materials. The complexes were analyzed by IR, UV–Visible, MS, NMR of 1H, 13C, 119Sn. The complex 3a was structurally identified by X-ray crystallography, which revealed a dimeric arrangement where the tin atom possess a distorted hexacoordinated environment in which the deprotonated phenolic oxygen atoms and the nitrogen atom of the azomethine from the ligand are coordinated to the metallic center, and one of the phenoxy oxygens bridges with the tin through an intermolecular interaction forming a planar Sn2O2 core. As strategy of molecular design, isosteric and bioisosteric replacement of halogens were employed. All organotin compounds were assessed for their in vitro cytotoxic activity on cancer cell lines K‐562 (chronic myelogenous leukemia), U‐251 (glioblastoma), HCT‐15 (human colorectal cancer), MCF‐7, MDA-MB-231 (human breast cancer), and SKLU‐1 (non‐small‐cell lung cancer). They evidenced an elevated cytotoxic activity, and the inhibitory percentage values stated higher activity than the cis-platin. The K-562 and MDA-MB-231 cells were more sensitive to organotin (IV) complexes than HCT-15 and MCF-7. The organotin (IV) compounds were also tested in vivo for brine shrimp lethality to examine their toxic properties.

The synthesis, characterization and catalytic evaluation of a series of NHC-Ni(II) complexes 1-Ni (-Me), 2-Ni (-nBu) and 3-Ni (-Bn) bearing a phthalimide fragment and a cyclopentadienyl (Cp) ligand is reported. The complexes were evaluated in C S couplings of iodobenzene and a range of thiols. The reactions were carried out using a catalyst loading of 5 mol % in DMF during 0.5–19 h. Being complex 2-Ni the one exhibiting the best activity for these transformations yielding up to 96% of products in 0.5 h.

Through experimental and computational studies we were able to prove that the hydrogen atom of the imine group forms structurally relevant C–H···F hydrogen bonds and that the fluorine atoms in the ...

Reactions of group 10 transition metals with the ditopic ligand dipicolyldithiocarbamate (DPDTC) were performed. Thus, 1:2 reactions of [Ni(CH3COO)2], [Pd(COD)Cl2] or [Pt(COD)Cl2] with DPDTC produced monomeric complexes of the type [M(κ2-SCS-DPDTC)2, M = Ni (1), Pd (2) or Pt (3)] with the dithiocarbamate ligand (DTC) coordinated in a typical chelate κ2-SCS fashion. Interestingly, the reaction of [NiCl2] with DPDTC, under similar conditions, afforded the organic compound 2-(pyridin-2-ylmethyl)imidazo[1,5-a]pyri-dine-3(2 H)-thione (4) as unique product. In order to prove the ditopic nature of the ligand DPDTC, complex [Pd(κ2-SCS-DPDTC)2] (2) was further reacted with [ZnCl2] in a 1:2 M ratio to yield the trinuclear complex [Cl2Zn(κ2-NN-DPDTC-SCS-κ2)Pd(κ2-SCS-DPDTC-NN-κ2)ZnCl2] (5). The molecular structures of all compounds were determinate by typical analytical techniques including the unequivocal determination of all structures by single crystal X-ray diffraction analysis. As expected, complexes 1–3 are isostructural, and the metal centres exhibiting slightly distorted square-planar geometries. While in 5, the trinuclear nature of the complex in confirmed exhibiting a nice combination of tetrahedral-square planar-tetrahedral geometries for the Zn-Pd-Zn centres respectively. Keywords: Dithiocarbamate, Metal-sulphur complexes, Trinuclear complexes, Ditopic ligands, Hetero-aromatic compound, Di-(2-picolyl)amine cyclization

Zinc(II) and cadmium(II) complexes of general formula [M(iPr2P(X)NC(Y)NC5H10-κ2-X,Y)2] (M = Zn, X = Y = S (4), X = S, Y = O (5), X = O, Y = S (6), and M= Cd, X = Y = S (7), X = S, Y = O (8), X = O, Y = S (9)) have been synthesized and characterized by using elemental analysis, IR and NMR spectroscopy, and thermogravimetric analysis (TGA). SCXRD molecular structures of complexes 6, 7, and 9 revealed ligand binding to the metal center in a bidentate fashion in an overall distorted tetrahedral coordination geometry. TGA showed that 4–9 decompose in a single step to their corresponding metal sulfides. Aerosol assisted chemical vapor deposition (AACVD) at 450 °C and subsequent annealing at 600 °C were used to examine 4–9 as single source precursors (SSPs) for the deposition of nanostructured metal sulfide thin films (4F–6F unannealed ZnS films and 7F–9F unannealed CdS films). GIXRD confirmed that the resultant films have a nanocrystalline hexagonal structure with the (002) preferential orientation, except for 9F, and the grain size varied from 15 to 24 nm. Scanning electron microscopy and atomic force microscopy (SEM and AFM) images revealed a relatively dense grain columnar structure. The elemental composition and mapping studies showed that the near-stoichiometric MS thin films are homogeneously distributed. The as-deposited ZnS thin films (4F–6F) displayed phosphorus content between 6.4 and 8.2%, while CdS films showed no phosphorus content except for 9F, which showed P 2%. The optical properties of the films such as direct optical energy gap (Eg), and Raman and photoluminescence (PL) spectra displayed some differences related to the employed SSP, being more significant for films obtained from precursors containing the hybrid ligand –P(O)NC(S)– (3), which showed a major phosphorus content (6F and 9F). A sharp excitonic emission at room temperature, as well as multiple Raman overtones, shows the high optical quality of the investigated CdS thin films. The PL spectra of ZnS films showed emissions attributed to the near band edge and different crystalline imperfections such as vacancies and interstitials.

Estrogens that are used as contraceptives or in replacement therapy are associated with an increase in the risk for developing thrombosis, mainly during the first year of treatment and in women with associated risk factors.To synthesize, characterize and identify the anticoagulant, antiplatelet aggregation and microvesicle-reducing effect of the new aminoestrogen Tyrame.CD1 strain mice were used, which had Tyrame (0, 1 and 2 mg/100 g) subcutaneously administered. At 24 h, a blood sample was obtained to determine whole-blood clotting time, microvesicles concentration and inhibitory effect on platelet aggregation.Blood clotting time increased up to 1.5 times in comparison with the control. Platelet aggregation inhibition had different magnitude depending on the agonist agent employed, and was complete with collagen. Both effects had a dose-dependent relationship. The microvesicles decreased up to six times with respect to the control.Tyrame reduces platelet aggregation and microvesicle formation, which emphasizes its potential therapeutic utility as an estrogen free of thrombotic effects.Los estrógenos empleados como anticonceptivos o en la terapia de sustitución se asocian a un incremento en el riesgo de desarrollar trombosis, principalmente durante el primer año de tratamiento y en mujeres con factores de riesgo asociados.Sintetizar, caracterizar e identificar el efecto anticoagulante, antiagregante plaquetario y reductor de las microvesículas del nuevo aminoestrógeno tyrame.Se emplearon ratones cepa CD1 a los que se les administró por vía subcutánea tyrame (0, 1 y 2 mg/100 g). A las 24 h se tomó una muestra de sangre para determinar el tiempo de coagulación en sangre total, la concentración de microvesículas y el efecto inhibidor de la agregación plaquetaria.El tiempo de coagulación en sangre se incrementó hasta 1.5 veces con respecto al control. La inhibición de la agregación plaquetaria tuvo diferente magnitud dependiendo del agente agonista, siendo completa con colágena. Ambos efectos siguieron una relación dependiente de la dosis. Las microvesículas disminuyeron hasta seis veces con respecto al control.el tyrame disminuye la agregación plaquetaria y la formación de microvesículas, lo que acentúa su posible utilidad terapéutica como un estrógeno sin efectos trombóticos.

The semisynthesis of novel derivatives of lupeyl palmitate and 3β-palmitoyloxy-olean-12-ene by introduction of a pyrazine at C-2 / C-3 and modifications of the relatively unexplored C-30 position of lupeol derivatives was conducted, and their cytotoxic and anti-inflammatory activities were evaluated. The derivatives 7, 10 and 11 significantly inhibited the tumor cell lines U251, K562, HCT-15, MCF-7 and SKLU-1, and compounds 7 and 11 were more active (IC

Background: Ischemic heart disease, cerebrovascular accident, and venous thromboembolism have the presence of a thrombotic event in common and represent the most common causes of death within the population. Objective: Since Schiff base copper(II) complexes are able to interact with polyphosphates (PolyP), a procoagulant and potentially prothrombotic platelet agent, we investigated the antiplatelet aggregating properties of two novel tridentate Schiff base ligands and their corresponding copper( II) complexes. Methods: The Schiff base ligands (L1) and (L2), as well as their corresponding copper(II) complexes (C1) and (C2), were synthesized and characterized by chemical analysis, X-ray diffraction, mass spectrometry, and UV-Visible, IR and far IR spectroscopy. In addition, EPR studies were carried out for (C1) and (C2), while (L1) and (L2) were further analyzed by 1H and 13C NMR. Tests for antiplatelet aggregation activities of all of the four compounds were conducted. Results: X-ray diffraction studies show that (L1) and (L2) exist in the enol-imine tautomeric form with a strong intramolecular hydrogen bond. NMR studies show that both ligands are found as enol-imine tautomers in CDCl3 solution. In the solid state, the geometry around the copper(II) ion in both (C1) and (C2) is square planar. EPR spectra suggest that the geometry of the complexes is similar to that observed in the solid state by X-ray crystallography. Compound (C2) exhibited the strongest antiplatelet aggregation activity. Conclusion: Schiff base copper(II) complexes, which are attracting increasing interest, could represent a new approach to treat thrombosis by blocking the activity of PolyP with a potential anticoagulant activity and, most importantly, demonstrating no adverse bleeding events.

(−)-Sparteine sulfate is a stable salt of the quinolizidine chiral diamine alkaloid (−)-sparteine. This compound, in addition to presenting various biological activities, has successfully been used...

The synthesis and characterization of a series dipalladium(I) complexes of formulae [Pd{1-[2′-(methoxycarbonyl)phenyl]-3-[4′-X-phenyl]triazenide}]2 [X = F (4), Cl (5), Br (6)] are reported. The crystal structure of complex 4 was determined by X-ray diffraction studies. The previously reported dipalladium(I) 1–3 as well as the new complexes 4–6 were used as catalysts in the Heck and Suzuki couplings of different p-substituted bromobenzenes.

The title compound crystallizes with two independent mol­ecules in the asymmetric unit. In the crystal, mol­ecules are linked by N—H⋯O hydrogen bonds, C—H⋯π, I⋯S and I⋯I inter­actions into a three-dimensional network., Two crystallographically independent mol­ecules (A and B) are present in the asymmetric unit of the title compound, C11H9IN2OS, which differ mainly in the dihedral angle between the phenyl and thia­zole rings [38.94 (16) and 32.12 (15)°, respectively]. In the crystal, the mol­ecules form ⋯A⋯B⋯A⋯B⋯ chains along the [001] and [010] directions through moderate N—H⋯O hydrogen bonds and C—H⋯π inter­actions, respectively. The overall three-dimensional network is formed by I⋯I and I⋯S inter­actions. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯C/C⋯H (26.2%), H⋯H (20.9%), H⋯I/I⋯H (19.4%) and H⋯O/O⋯H (6.8%) inter­actions.

Cuautepestalorin (4), a 7,8-dihydrochromene-oxoisochromane adduct bearing a spiro-polycyclic (6/6/6/6/6/6) ring system, along with its putative biosynthetic precursors, cytosporin M (1), cytosporin N (2), and oxopestalochromane (3), were isolated from the bioactive extract of Pestalotiopsis sp. using a combination of molecular networking and dereplication techniques. Their structures were elucidated using a set of spectroscopic, spectrometric, chiroptical (experimental and theoretical), and X-ray crystallography data. Compounds 3 and 4 exhibited modest potency when evaluated in vitro as α-glucosidase inhibitors.

We evaluated thiourea organocatalysts that incorporate a chiral group which includes a trifluoromethyl moiety and contrasted their performance with non-fluorinated analogs. The comparison between such systems allows the direct study of the NH acidity of a thiourea bonded to an aliphatic substituent. In principle, -CF3 systems feature an enhanced hydrogen bond (HB) donor capacity that is undoubtedly beneficial for HB-catalysis applied to the Baylis-Hillman reaction. We found that the thiourea substituted on both nitrogens with this group accelerates this reaction like Schreiner's thiourea. On the other hand, we observed a different behavior in reactions promoted by bifunctional catalysts (thiourea-primary amine). In the Michael addition of isobutyraldehyde to methyl benzylidenepyruvate, the -CF3 containing catalysts were better than the -CH3 systems, whereas the conjugate addition to N-phenylmaleimide showed the opposite behavior. Theoretical calculations of the transition states indicated that the phenylethyl group in fluorinated and non-fluorinated compounds have different kinds of interactions with the electrophile. These interactions are responsible for a different arrangement of the electrophile and thereby the selectivity of the catalyst. Therefore, it cannot be generalized that in all cases NH acidity correlates with the performance of the catalyst, particularly, with aliphatic substituents that unlike the aromatic ones possess groups that are outside the plane of the thiourea.

The synthesis of four novel non-symmetric Ni(II)-POCOP pincer complexes meta-functionalized with either benzothiazole or benzimidazole at the central aryl ring is described. All complexes were fully characterised in solution by various analytical techniques and the molecular structures in the solid state of complexes 1b, 2a and 2b were unequivocally determined by single crystal X-ray diffraction analysis. In addition, the Ni(II)-POCOP pincer complexes were efficiently used as catalysts in the synthesis of diarylketones by cross-coupling reactions of functionalized benzaldehydes and boronic acid derivatives under relatively mild conditions. An important aspect of this transformation is the dependence on the steric properties of the donor groups (OPR2) of the pincer ligands, the more active compounds having the phosphinitos bearing isopropyl groups (1a and 2a) than those containing tert-butyl substituents (1b and 2b).

In this paper, we designed and extended modification basing on the flutamide structure. A series of flutamide-conjugates were obtained with methyl bromoacetate and ethylenediamine. Through the synthesis of two conjugates with 3,5-bis(dodecyloxy)benzoate derivatives, these flutamide conjugates were tested for anticancer activity. Among the compounds tested, the flutamide-conjugates showed good inhibition activity against cancer cell lines U-251, PC-3 and K-562. The conjugates showed a better inhibitory effect than free flutamide and did not show activity against normal COS-7 monkey kidney fibroblast cells. It was also observed that the flutamide conjugates had an inhibitory effect against human colorectal adenocarcinoma HCT-15.

Hypoxylon species are distributed worldwide and have been isolated from different habitats. The endophyte Hypoxylon anthochroum strain Gseg1 was isolated from healthy leaves of Gliricidia sepium. A chemical study of the culture medium and mycelium organic extracts of the endophytic fungus H. anthochroum Gseg1 led to the isolation of three known isobenzofuranones, 7-hydroxy-4,6-dimethyl-3H-isobenzofuran-1-one, 1, 7-methoxy-4,6-dimethyl-3H-isobenzofuran-1-one, 2, 6-formyl-4-methyl-7-methoxy-3H-isobenzofuran-1-one, 3, and one compound was isolated for the first time as a natural product, 7-methoxy-4-methyl-3H-isobenzofuran-1-one, 4. In addition, the chemical synthesis of 1 and 2, and a derivative, 7-methoxy-6-methyl-3H-isobenzofuran-1-one, 5, was performed. The isobenzofuranones showed antifungal and antioomycete activities. Compounds 1-5 inhibited the growth of Fusarium oxysporum, Alternaria alternata, Pythium aphanidermatum, and Phytophthora capsici, in addition, 1, 2 and 5 interrupted the respiration and caused electrolyte leakage due to cell membrane damage. Compound 2 was the most active, inhibiting the growth of the four microorganisms, affecting the respiration and increasing the relative conductivity due to electrolyte leakage. Compounds 1-4 also induce morphological changes in the plant pathogens' mycelia and hyphae. These compounds could be useful for the control of plant pathogenic fungi and oomycetes of agricultural relevance.

A new blue photoluminescent 2D metal&ndash, organic framework, 1, with formula {[Zn2(&mu, 2-BDC)2(iQ)2]}&infin, has been synthesized in a high yield under solvothermal conditions by reacting Zn(II) ions with 1,4-benzenedicarboxylic acid (H2BDC) and isoquinoline (iQ) in DMF. Compound 1 was thoroughly characterized by single-crystal X-ray diffraction, solid-state cross-polarization magic-angle spinning 13C NMR, X-ray powder diffraction, scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), and thermoanalysis. The crystal structure of 1 showed interpenetrated 2D frameworks consisting of dinuclear paddle-wheel cores Zn2, moreover, this material possessed thermostability up to 310 &deg, C. The CPMAS 13C-NMR spectrum of 1 is consistent with the symmetry of the crystal structure. Luminescence studies showed that 1 strongly enhances its fluorescence emission in the presence of xylene isomers with a pronounced selectivity to p-xylene.

The aerial parts of Salvia cinnabarina afforded two undescribed labdane diterpenoids 1 and 2 (malonylcommunol and 6&beta, hydroxy-trans-communic acid) along with two known labdane diterpenoids, trans-communic acid (3) and trans-communol (4). Additionally, seven known metabolites were also isolated, two isopimarane diterpenoids 5 and 6, two sesquiterpenoids identified as &beta, eudesmol (7) and cryptomeridiol (8), and three aromatic compounds identified as phthalic acid (9), a mixture of tyrosol fatty acid esters (10) and the flavone salvigenine (11). While compounds compounds 1&ndash, 3 showed significant inhibition of yeast &alpha, glucosidase, compounds 2, 3 and 7 had no anti-inflammatory activity in the edema model induced by TPA. This paper is not only the first report on a wild population of Salvia cinnabarina, but also of the presence of labdane-type diterpenoids in a Mexican Salvia sp.

Methods: The synthesis of conjugates of flutamide with resorcinarene-PAMAM-dendrimers as well as alkyl and ethyl phenyl chains in the lower part of the macrocycle as a nucleus and diethylenetriamines in the dendritic branches gives the opportunity to obtain conjugates in one step of synthesis with 16 and 64 flutamide moieties in the structure. Results: The in vitro anticancer studies showed that the conjugates of flutamide are more active than the free flutamide and the flutamide derivatives, thus diminishing the amount of flutamide used. The resorcinarenedendrimer- flutamide conjugates with a high drug payload improve the activity of the drug. Conclusion: This is important in delivering a sufficient amount of flutamide and suggests that the dendrimer facilitates more of the drug being introduced into cells. It was also observed that the new conjugates are less toxic than the anti-androgens.

The synthesis of bis(N-methylbenzimidazol-2-yl)methane serves as the entry point for the preparation of a tetrabenzimidazole-based binucleating ligand. A cupric complex of the former compound was prepared to compare its properties to those of the dicopper complexes of the tetrabenzimidazole derivative. In the latter case, the reaction of the binucleating ligand with cupric trifluoromethylsulfonate in air results in intramolecular C H activation with concomitant hydroxylation, presumably by an in situ formed copper-oxygen reactive intermediate. This reactivity highlights the relevance of benzimidazole-based scaffolds in biologically inspired copper-oxygen systems.

A new non-symmetric phosphinito-thiophosphinito POCSP-Ni(II) pincer compound was synthetized and characterized. The molecular structure of [NiCl{C6H3-2-(OPPh2)-6-(SPPh2)}] (1) was unequivocally determined by single crystal X-ray diffraction analysis, showing the Ni center to be located into a slightly distorted square planar geometry. This compound was used as efficient catalyst in C-S couplings of disulfides with iodobenzenes, exhibiting good activity and selectivity as well as tolerance to different functional groups.

Previous report described that CHCl3:MeOH extract ofC. chayamansaleaves and pure compounds (moretenol, moretenyl acetate, kaempferol-3,7-dimethyl ether, and 5-hydroxy-7-3′,4′-trimethoxyflavanone) showed important topical and systemic anti-inflammatory activity in acute model, as well asin vitroantimycobacterial and antiprotozoal activities. In this paper, we describe thein vivohepatoprotective and anti-inflammatory effects of the CHCl3:MeOH extract in chronic model and the isolation of additional compounds (moretenone and lupeol acetate). The hepatoprotective activity was determined at 39 days using Balb/c mice with liver damage induced with an antitubercular drug (RIF/INH/PZA). The anti-inflammatory activity was evaluated in a chronic model induced with CFA and in two acute models (TPA and carrageenan). In addition, moretenone and lupeol acetate were isolated and identified by spectroscopic data. Lupeol acetate is a main compound present in fractions 14-42, and this fraction was the majority fraction from the extract; from this moretenone was obtained. In animals with liver damage, the extract at 200 and 400 mg/kg induced better body weight gain with respect to positive control (Silymarin); in addition, the mice that received the extract at 200 mg/kg and Silymarin exhibited slight steatosis; however, the animals’ livers at 400 mg/kg did not show steatosis. The extract and fractions 14-42 showed a good anti-inflammatory activity by TPA model (DE50= 1.58 and 1.48 mg/ear) and by carrageenan model (DE50= 351.53 and 50.11 mg/kg). In the chronic inflammatory test, the extract at three doses revealed a similar effect to that of phenylbutazone, although the body weight gain was better in animals that received the extract at 900 mg/kg.Conclusion. The CHCl3:MeOH extract showed significant anti-inflammatory and good hepatoprotective effect on chronic models. The fraction containing moretenone and lupeol acetate as main compounds was more active than extract in both acute models of inflammation.

Pyridylthiother-ligated Pd(II) complexes have been synthesized and efficiently applied in Suzuki-Miyaura couplings using microwave irradiation in DMF and water. The pyridylthioether NS (NS1 and NS2) and pyridyldithiother (SNS) ligands and their corresponding palladium complexes Pd-NS1, Pd-NS2, Pd-SNS were easily synthesized and fully characterized by various analytical techniques. The molecular structures of the ligand SNS and the Pd(II) complexes Pd-NS2, Pd-SNS were unequivocally determined by single crystal X-ray diffraction analysis. From these compounds, complex Pd-SNS exhibits the ligand SNS coordinated in a N,N-bidentated rather than the typical SNS-pincer manner in the solid state, giving place to a seven membered palladacycle whereas in solution it behaves as a typical SNS-pincer complex. This compound was also found to be the most efficient catalyst of the series of complexes in Suzuki-Miyaura couplings with different p-substituted aryl bromides.

The synthesis and characterization of a series of SPS–Ni(II) pincer complexes with different para-substituted triphenylphosphines has been performed. The molecular structure of [Ni(phPS2)(PPh3)] (1) (phPS2H2 = PhP(C6H4-2-SH)2, bis(phenyl-2-thiol)phenylphosphine) was unequivocally determined by single crystal X-ray diffraction analysis. The metal centre exhibited a slightly distorted square planar geometry. The complexes showed a high catalytic activity in the C S cross-coupling reaction of both alkyl- and aryl-disulfides with iodobenzenes for the production of non-symmetric sulfides. In general, the different para-substituted triphenylphosphine ligands do not affect the catalytic performance of the SPS–Ni(II) complexes. However, activity of the catalyst decreases with the steric hindrance of the different alkyl groups in the disulphide substrates.

The preparation and characterization of two series of organotin(IV) complexes are reported, each series differing in the nature of the substituent bonded to the tin atom (cyclohexyl or bis(trimethyl)silylmethyl). The isosteric and bioisosteric approach was used as the strategy of molecular design. The ligand was 5-hydroxymethyl-4-[(2-hydroxyphenyl)iminomethyl]-2-methylpyridin-3-ol substituted at position 4 by methyl, halogeno (F, Cl), methoxy, nitro and tert-butyl; the synthesis of the organotin(IV) complexes was performed by a multi-component strategy in reasonable to high yields depending on the nature of the ligand. All new complexes were fully characterized by IR, MS, X-ray determinations and NMR (1H, 13C, 119Sn). Crystallographic data of complexes showed the geometries adopted around the metal tin center varied between square pyramidal in 2c and a trigonal bipyramidal in 3b-3d with the alkyl groups in the trigonal plane and the two oxygen atoms in the equatorial plane. Additionally, the in vitro cytotoxicity tests of the complexes towards six types of human cancerous cell lines U-251 (glioblastoma), K-562 (chronic myelogenous leukemia), HCT-15 (human colorectal), MCF-7 (human breast), MDA-MB-231(human breast) and SKLU-1 (non-small cell lung) showed the superior activity of the organotin complexes compared to the corresponding cisplatin used as positive control. The complexes containing fluorine exhibited excellent IC50 data indicating that both the bioisosteric replacement and the cyclohexyl ring bonded to the tin atom increased the potency of the cytotoxic activity towards the cancer cell lines tested.

The title compound, C30H44O3[systematic name: 6aR,6 bR,8aS,9aR,12aR,14bR)-4,4,6a,6;b,8a,14b-hexamethyl-12-methyleneicosahydro-3H-phenanthro[1′,2′:6,7]indeno[2,1-b]furan-3,11(2H)-dione], is a triterpene lactone, which was isolated from dichloromethane extract ofElaeodendron trichotomum(Turcz.) Lundell (celastraceae) stem bark. The compound has a lupane skeleton and consists of four fused six-membered rings and two five-membered rings. In the crystal, molecules are linked by weak C—H...O hydrogen bonds into a three-dimensional network. The configuration of ochraceolide A was proposed based on analogue compounds which belong to the lupane type.

The synthesis and characterization of triazenes of the type 1-[2′-(methoxycarbonyl)phenyl]-3-[4′-X-phenyl]triazene [X = F ( 1 ), Cl ( 2 ), Br ( 3 ), I ( 4 )] as precursors of triazenide ligands for the preparation of their complexes of formula [Ru{1-(2′-methoxycarbonylphenyl)-3-(4′-X-phenyl)triazenide}(Cl)( p- cymene)] [X = F ( 6 ), Cl ( 7 ), Br ( 8 ), I ( 9 ), CH 3 ( 10 )] are reported. Molecular structures for all four triazenes ( 1 – 4 ), and of complexes 6 , 9 and 10 were determined by X-ray diffraction studies. Complexes 6 – 10 were tested as catalysts in the transfer hydrogenation of acetophenone in the presence and in the absence of base. The best results were obtained in the presence of base with yields in the range of 86–94%, whereas even in the absence of base yields in the range 42–65% were achieved.

A series of Ni(II) and Pt(II) complexes with DTC ligands including a hydrophilic ethanol moiety [N-(R)ethanolamine (R = Me(1), Et(2), iPr(3), Bn (4))] have been prepared and fully characterized. The antitumor activity of the Pt(II) derivatives has been evaluated against different cancer cell lines, showing complex 4-Pt (including N-(benzyl)ethanolamine DTC ligand DTC-4) to be the most active of the series, exhibiting 100% inhibition on glial cells of nervous central system (U251), leukaemia (K562), colon (HCT-15), breast (MCF-7) and lung (SKLU-1). Finally, the Ni(II) derivatives were explored as catalyst in Suzuki-Miyaura couplings, however only decomposition of the complexes was observed with null conversions to biphenyls.

Porphyrins meso -substituted with p -phenylene vinylene (OPV) were synthesized. The porphyrin dendrimers obtained showed a strong dependence on the type of connection of the dendritic branches. In the instance of the all trans -conformation linkages, an H-type aggregate is obtained for the linear OPV and strong J-aggregate for the ramified OPV. An adequate intramolecular energy transference stemming from the OPVs (donors) to the respective cores was observed. Furthermore, the number oligo( p -phenylene vinylene) (OPV) groups linked to the porphyrin system increase the energy transfer efficiency. This behavior also was observed in the photovoltaic studies.

We report for the first time the high sorption properties of a molecular rotor with no permanent voids or channels in its crystal structure. Such crystalline phase originates from THF, DCM, or the irreversible desolvation of entrapped benzene molecules. From these, the benzene in its solvate form acts as rotation stopper, as supported by dynamic characterization using solid-state 2H NMR experiments. In the solvent-free form, the diffusion of small quantities of iodine vapors caused a significant change in the intramolecular rotation, increasing the known activation energy to rotation from 8.5 to 10.6 kcal mol–1. Notably, those results paved the way for the discovery of the high CO2 uptake (201.6 cm3 g–1 at 196 K, under 1 atm) and acetone (5 wt %), a sorption property that was attributed to both, the restriction of the molecular rotation at low temperatures and the flexibility of the molecular axle made of conjugated p-(ethynylphenylene), surrounded by carbazole.

Two new Hg(II) and Cd(II) one-dimensional coordination polymers have been constructed from metal iodide and a N, N′-Bis-pyridin-4-ylmethylene-naphthalene-1,5-diamine ligand using conventional methods. The effects of the ligand geometry and the coordination modes of iodide on the structures of the coordination polymers have been discussed in detail. In order to clarify the effect of experimental conditions on the morphology and size of [Cd(L)I2]n (1) and [Hg(L)I2]n particles, we have systematically investigated the influence of concentration and sonication power on the size of the resulting products for the aim of realizing controllable synthesis. The results indicated that the concentration and sonication power directly influenced the final size of nanostructures of these coordination polymers. The prepared nanocrystals of these two coordination polymers were analyzed using scanning electron microscopy, infrared spectroscopy and X-ray powder diffraction.

In this paper, we present the use of the interaction between aromatic rings—usually called π–π interaction—as the main tool in the organization of coordination complexes in a crystal. To do so, we selected coordination compounds with aromatic rings pointing outside the molecules to favor their self-assembly through these interactions. Here, we report the molecular and crystal structures of three Cu(II) complexes: [Cu2(terpy)2(bz)2](ClO4)2 (1), [Cu2(terpy)2(tfipth)2] (2) and [Cu4(terpy)4(tfipth)2(ClO4)2](ClO4)2 (3), where terpy = 2,2′:6′,2′′ terpyridine, bz = benzoate and tfipth = tetrafluoro-isophthalate. In the three crystals, the interaction between aromatic rings organizes molecules in chains that closely pack with disordered anions or water molecules located in the space between the chains. A study of the Crystal Structure Database (CSD) indicates that the main interaction in terpy molecules is between a lateral ring and the central ring of different molecules and when terpy molecules point in opposite directions, they tend to form chains, suggesting that these interactions can be used as a design tool. The metal complexes were designed to obtain a square pyramidal structure around the metal ion, but we observed a contact between the non-coordinated O (carboxylate) and the Cu(II) ion. We studied the presence of this interaction and its nature with computational chemistry.

Previously non-isolated compounds (scopoletin and β-D-Glucopyranoside, (1R)-O-isopropyl 6-O-(2,3,4-tri-O-acetyl-β-D-xylopyranosyl)-2,3,4-triacetate) were isolated from an organic extract of the Cnidoscolus chayamansa stem. Also, lupeol acetate (main compound, 49.7 mg/g of dry extract) and scopoletin (0.19 mg/g of dry extract) were quantified by HPLC analysis from this organic extract.The protective activity of the C. chayamansa organic extract against hepatotoxicity induced by antitubercular drugs [Rifampicin (50 mg/kg), Isoniazid (50 mg/kg), and Pyrazinamide (100 mg/kg)] are reported. The extract was tested at 200 and 400 mg/kg in Balb/C mice during 85 days, using silymarin (2.5 mg/kg) as positive control. Liver damage was determined using biochemical parameters (AST, ALT, ALP, CHOL, HDL TG, Urea, and CREA), histological analysis, and evaluation of oxidative stress (SOD, CAT, Gpx, Lpx and POx). The extract at both doses favored body weight gain with respect to the anti-TB group; the dose of 200 mg/kg was better. Also, the extract at both doses decreased the values of transaminases (AST, ALT) enzymes (p

The compound (E)-N-(2,4-difluorophenyl)-1-(4-pyridinyl)methanimine monohydrate (1) was synthesized, characterized spectroscopically and by X-ray crystallography. 1 crystallizes in the non-centrosymmetric C2 space group with Z=4 (two organic molecules, 1a and 1b, and two water molecules). The crystal structure presents O–H···N, non-classical C–H···X hydrogen-bonds, and π–π stacking interactions. Hirshfeld Surface studies confirmed these interactions. The main intermolecular interactions are the π–π between the pyridine and the fluorinated ring of molecules stacking in columns (1a with 1a and 1b with 1b) and the O–H···N H-bonds. The imine acts as a H-bond-donor to the water molecules and a H-bond-acceptor of the water molecule's hydrogen atoms. The energy frameworks show significant interactions between molecules that are not easy to identify by geometric parameters, indicating the convenience of energy calculations to understand crystal structures better.

Bioactivity-directed fractionation of the combined culture medium and mycelium extract of the endophytic fungus Xylaria feejeensis strain SM3e-1b, isolated from Sapium macrocarpum, led to the isolation of three known natural products: (4S,5S,6S)-4-hydroxy-3-methoxy-5-methyl-5,6-epoxycyclohex-2-enone or coriloxine, 1; 2-hydroxy-5-methoxy-3-methylcyclohexa-2,5-diene-1,4-dione, 2; and 2,6-dihydroxy-5-methoxy-3-methylcyclohexa-2,5-diene-1,4-dione or fumiquinone B, 3. This is the first report of compound 3 being isolated from this species. Additionally, four new derivatives of coriloxine were prepared: (4R,5S,6R)-6-chloro-4,5-dihydroxy-3-methoxy-5-methylcyclohex-2-enone, 4; 6-hydroxy-5-methyl-3-(methylamino)cyclohexa-2,5- diene-1,4-dione, 5; (4R,5R,6R)-4,5-dihydroxy-3-methoxy-5-methyl-6-(phenylamino)cyclohex-2-enone, 6; and 2-((4-butylphenyl)amino)-5-methoxy-3-methylcyclohexa-2,5-diene-1,4-dione, 7. X-ray analysis allowed us to unambiguously determine the structures and absolute configuration of semisynthetic derivatives 4, 5, and 6. The phytotoxic activity of the three isolated natural products and the coriloxine derivatives is reported. Germination of the seed, root growth, and oxygen uptake of the seedlings of Trifolium pratense, Medicago sativa, Panicum miliaceum, and Amaranthus hypochondriacus were significantly inhibited by all of the tested compounds. In general, they were more effective inhibiting root elongation than suppressing the germination and seedling oxygen uptake processes as shown by their IC50 values.

Herein we report the synthesis of the highly stable crystalline carbazole-based rotor 3 with simultaneous rapid solid state internal rotation and good fluorescence emission. Single crystal and powder X-ray diffraction studies along with microscopy revealed a phase transition from a labile benzene solvate (phase I) to highly stable crystals (phase II) that feature fast intramolecular rotation in the megahertz regime at room temperature, according to variable temperature 2H solid state NMR experiments using isotopically enriched analogues. In addition to the megahertz rotation within its crystals, this crystal phase II displays enhanced solid state fluorescence with a higher quantum yield of ϕ = 0.28, relative to the emission of this compound in THF solution (ϕ = 0.06). These two solid state properties are significantly different from shorter compounds 1 and 2 (static and nonemissive) included here for comparison purposes.

In the title salt, each cation shows a moderate distortion between the planes of the amide groups and the quinolinium rings. The tri­fluoro­methane­sulfonate anions are linked to organic cations via N—H⋯O hydrogen-bonding inter­actions involving the NH amide groups. In the crystal, weak C—H⋯O hydrogen bonds and π-stacking inter­actions between the quinolinium and phenyl rings link the organic cations into chains., In the title compound, C23H18N3O3 +·CF3SO3 −, the asymmetric unit contains two crystallographically independent organic cations with similar conformations. Each cation shows a moderate distortion between the planes of the amide groups and the quinolinium rings with dihedral angles of 14.90 (2) and 31.66 (2)°. The quinolinium and phenyl rings are slightly twisted with respect to each other at dihedral angles of 6.99 (4) and 8.54 (4)°. The tri­fluoro­methane­sulfonate anions are linked to the organic cations via N—H⋯O hydrogen-bonding inter­actions involving the NH amide groups. In the crystal, the organic cations are linked by weak C—H⋯O(nitro group) inter­actions into supramol­ecular chains propagating along the b-axis direction.