A pH-Sensitive Fluorescent Chemosensor Turn-On Based in a Salen Iron (III) Complex: Synthesis, Photophysical Properties, and Live-Cell Imaging Application.

pH regulation is essential to allow normal cell function, and their imbalance is associated with different pathologic situations, including cancer. In this study, we present the synthesis of 2-(((2-aminoethyl)imino)methyl)phenol (HL1) and the iron (III) complex (Fe(L1)2Br, (C1)), confirmed by X-ray diffraction analysis. The absorption and emission properties of complex C1 were assessed in the presence and absence of different physiologically relevant analytes, finding a fluorescent turn-on when OH- was added. So, we determined the limit of detection (LOD = 3.97 × 10-9 M), stoichiometry (1:1), and association constant (Kas = 5.86 × 103 M-1). Using DFT calculations, we proposed a spontaneous decomposition mechanism for C1. After characterization, complex C1 was evaluated as an intracellular pH chemosensor on the human primary gastric adenocarcinoma (AGS) and non-tumoral gastric epithelia (GES-1) cell lines, finding fluorescent signal activation in the latter when compared to AGS cells due to the lower intracellular pH of AGS cells caused by the increased metabolic rate. However, when complex C1 was used on metastatic cancer cell lines (MKN-45 and MKN-74), a fluorescent turn-on was observed in both cell lines because the intracellular lactate amount increased. Our results could provide insights about the application of complex C1 as a metabolic probe to be used in cancer cell imaging.

Spectroscopy, molecular structure, and electropolymerization of Ni(II) and Cu(II) complexes containing a thiophene-appending fluorinated Schiff base ligand.

In this contribution, we describe the preparation, characterization, and electrochemical behavior of a series of four new mononuclear M(II) complexes featuring a symmetric substituted N2O2-tetradentate Schiff base ligand, bearing either trifluoromethyl and p-bromophenyl (M = Ni, 3; Cu, 4) or trifluoromethyl and the π-extended p-(2-thienyl)phenylene (M = Ni, 5; Cu, 6) substituents. Complexes 3 and 4 were readily synthesized by reacting the diprotic fluorinated Schiff base proligand 2 with the appropriate hydrated metal(II) acetates, whereas 5 and 6 were obtained upon Stille cross-coupling reaction of 3 and 4 with 2-(tributylstannyl)-thiophene, respectively. Compounds 3-6 were isolated as neutral, air, and thermally stable-coloured solids, with yields ranging from 60 to 80%. The four complexes, the diimine precursor 1 and its trifluoroacetylated derivative 2, were identified using analytical (EA, ESI-MS), spectroscopic (IR, 1H, 13C, and 19F NMR), and X-ray crystallographic methods. X-ray crystal structure determination of complexes 3-5 revealed that both four-coordinate Ni(II) and Cu(II) metal ions adopt a square planar geometry. The magnetic properties of powdered samples of the Cu(II) derivatives 4 and 6 have been investigated (2-300 K) and found consistent in both cases with a single isolated copper(II) ion (s = 1/2). DFT calculations were used to examine the optimal geometries of complexes 5 and 6, allowing for a consistent perspective of their structure and characteristics. The primary aspects of the UV-vis spectra were interpreted using TD-DFT computations. Finally, electrochemical data indicate that complexes 5 and 6 polymerize at high anodic potentials in acetonitrile (greater than 2.0 V vs. Ag/AgCl). Cyclic voltammetry, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (SEM-EDS) analyses were used to characterize the obtained films poly-5 and poly-6.

Synthesis, characterisation, crystal structure and antimicrobial evaluation of novel 6-alkoxyergosta-4,6,8(14),22-tetraen-3-one derived from natural ergosta-5,7,22-trien-3ß-ol.

In this study, we report a facile transformation starting from 5α-hydroxyergosta-7,22-dien-3,6-dione (1) to afford two novel compounds: 6-methoxyergosta-4,6,8(14),22-tetraen-3-one (2) and 6-ethoxyergosta-4,6,8(14),22-tetraen-3-one (3) using alcoholic acid catalysis. Their structures were elucidated using NMR experiments, FT-IR, MS and X-ray analysis. These compounds were evaluated for antibacterial activity using the disk and broth diffusion test. In those tests, compound 3 was found to be the most significant antibacterial agent. In general, compounds 1-3 showed inhibition zone in the range of 7.00-12.3 mm for S. aureus and S. mutans, meanwhile for Gram-negative bacteria E. coli and Pseudomonas sp. was found to be in the range of 7.00-8.00 mm. For the most active, compound 3, MIC was significantly lower than that reported for ergosterol, in a value of 160 µg/mL. Overall, these compounds were more active than their natural precursor.

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer†.

The new cyrhetrenyl acylhydrazone [(CO)3 Re(η5 -C5 H4 )-C(O)-NH-N = C(CH3 )-(2-C4 H2 S-5-NO2 )] (E-CyAH) has been designed, synthesized and fully characterized to study the effect of having a cyrhetrenyl fragment (sensitizer) covalently bonded to an acylhydrazone moiety (switch), on its photophysical and photochemical properties. The crystal structure reveals that E-CyAH adopts an E-configuration around the iminic moiety [-N = C(CH3 )]. The absorption spectrum of E-CyAH displays two bands at 270 and 380 nm, which are mainly ascribed to π â†’ π* intraligand (IL) and dπ  â†’ π* metal-to-ligand charge transfer (MLCT) transitions, being consistent with DFT/TD-DFT calculations. Upon 365 nm irradiation, E-CyAH photoisomerizes to Z-CyAH, as evidenced by UV-Vis and 1 H-NMR spectral changes, with a quantum yield value ΦE -CyAH → Z -CyAH of 0.30. Z-CyAH undergoes a first-order thermal back-isomerization process, with a relatively short half-life τ1/2 of 277 min. Consequently, E-CyAH was quantitatively recovered after 24 h, making it a fully reversible T-type molecular photoswitch. This remarkable behavior allows us to measure the individual photophysical properties for both isomers. In addition, E-CyAH and Z-CyAH efficiently photosensitize the generation of singlet oxygen (O2 (1 Δg )) with good yield (ΦΔ  = 0.342).

Synthesis of 2-Deoxybrassinosteroids Analogs with 24-nor, 22(S)-23-Dihydroxy-Type Side Chains from Hyodeoxycholic Acid.

Natural brassinosteroids are widespread in the plant kingdom and it is known that they play an important role in regulating plant growth. In this study, two new brassinosteroid analogs with shorter side chains but keeping the diol function were synthesized. Thus, the synthesis of 2-deoxybrassinosteroids analogs of the 3α-hydroxy-24-nor, 22,23-dihydroxy-5α-cholestane side chain type is described. The starting material is a derivative from hyodeoxycholic acid (4), which was obtained with an overall yield of 59% following a previously reported five step route. The side chain of this intermediate was modified by oxidative decarboxylation to get a terminal olefin at the C22-C23 position (compound 20) and subsequent dihydroxylation of the olefin. The resulting epimeric mixture of 21a, 21b was separated and the absolute configuration at the C22 carbon for the main product 21a was elucidated by single crystal X-ray diffraction analysis of the benzoylated derivative 22. Finally, lactonization of 21a through a Baeyer-Villiger oxidation of triacetylated derivative 23, using CF3CO3H/CHCl3 as oxidant system, leads to lactones 24 and 25 in 35% and 14% yields, respectively. Deacetylation of these compounds leads to 2-deoxybrassinosteroids 18 and 19 in 86% and 81% yields. Full structural characterization of all synthesized compounds was achieved using their 1D, 2D NMR, and HRMS data.

New 1H-Benzo[f]indazole-4,9-diones Conjugated with C-Protected Amino Acids and Other Derivatives: Synthesis and in Vitro Antiproliferative Evaluation.

1H-Benzo[f]indazole-4,9-dione derivatives conjugated with C-protected amino acids (glycine, l-alanine, l-phenylalanine and l-glutamic acid) 6a-l were prepared by chemically modifying the prenyl substituent of 3-methyl-7-(4-methylpent-3-enyl)-1H-benzo[f]indazole-4,9-dione 2 through epoxidation, degradative oxidation, oxidation and N-acyl condensation reactions. The chemical structures of the synthesized compounds were elucidated by analyzing their IR, ¹H-NMR and (13)C-NMR spectral data together with elemental analysis for carbon, hydrogen and nitrogen. The preliminary in vitro antiproliferative activity of the synthesized derivatives was evaluated on KATO-III and MCF-7 cell lines using a cell proliferation assay. The majority of the derivatives exhibited significant antiproliferative activity with IC50 values ranging from 25.5 to 432.5 µM. These results suggest that 1H-benzo[f]indazole-4,9-dione derivatives are promising molecules to be researched for developing new anticancer agents.

[(η(5)-C5Me5)Ru](+) fragments ligated to polyaromatic hydrocarbons: an experimental and computational approach to pathways for haptotropic migration.

Ligand exchange reactions between [Cp*Ru(NCMe)3][PF6], where Cp* represents η(5)-C5Me5, and the polycyclic aromatic hydrocarbons (PAHs) pyrene, acenaphthylene and fluoranthene afforded the known [Cp*Ru(η(6)-pyrene)][PF6] (1) and the new mixed sandwiches [Cp*Ru(η(6)-acenaphthylene)][PF6] (2) and [Cp*Ru(η(6)-fluoranthene)][PF6] (3), respectively, isolated in quantitative yields (94-100%). Complex 3 is formed as a mixture of two isomers: 3A as the major product where the [Cp*Ru(+)] moiety is coordinated to the naphthalene fragment of fluoranthene, and 3B with the coordination of the arenophile to the peripheral benzene ring, in a 90/10 spectroscopic ratio. The composition and identity of the complexes were deduced by elemental analysis, (1)H and (13)C multidimensional NMR spectroscopy, and mass spectrometry. Compounds 1A, 3A and 2A have been characterized using X-ray structural investigations. That showed that the [Cp*Ru(+)] unit is η(6)-attached to one of the two naphthalene rings in each complex. Heating 1 and 3 at 90 °C in CD3NO2 solutions or heating 3 at 120 °C in the solid phase did not provide any evidence for thermally induced intramolecular inter-ring haptotropic rearrangements. These rearrangements were modelled by DFT calculations which indicated rather high activation energies.

(E)-1-(3-Bromo-phen-yl)-3-(3,4-dimeth-oxy-phen-yl)prop-2-en-1-one.

The mol-ecular structure of the title compound, C(17)H(15)BrO(3), consists of a bromo-phenyl and a 3,4-dimeth-oxy-phenyl group linked through a prop-2-en-1-one spacer. The C=C double bond displays an E conformation, while the carbonyl group shows an S-cis conformation relative to the double bond.

trans-Bis[1,2-bis-(diphenyl-phosphan-yl)ethane]-chlorido(ethyn-yl)ruthenium(II).

The mol-ecular structure of the title compound, trans-[Cu(C2H)Cl(C26H24P2)2], consists of an Ru(II) cation, located on an inversion centre, in an octa-hedral environment defined by two chelating phosphines, one acetyl-ide and one chloride ligand. The -C CH and the chlorine ligands are disordered over two equivalent positions (0.5 occupancy each). The coordination geometry is distorted octa-hedral, with the -C CH fragment and the Cl ligand in trans positions. The four P atoms occupy the equatorial plane of the octa-hedron and the chloride and acetyl-ide ligands the axial positions.

Heterobimetallic Re=Pd complexes bridged by eta(1):eta(5)-Ph(2)PC(5)H(4) ligand. Synthesis, electronic and crystal structure of (CO)(2)(PR(3))(eta(5)-C(5)H(4)PPh(2))Re-PdCl(2), R = Me and OMe.

The new rhenium complexes (eta(5)-C(5)H(4)PPh(2))Re(CO)(2)(PR(3)) (R = Me (1) and OMe (2)) were prepared photochemically from (eta(5)-C(5)H(4)PPh(2))Re(CO)(3) in the presence of PMe(3) or P(OMe)(3). Further reaction of these ligands with PdCl(2)(NCPh)(2) in chloroform, produces the heterobimetallic complexes (CO)(2)(PMe(3))(eta(5)-C(5)H(4)PPh(2))Re-PdCl(2) (3) and (CO)(2)(P(OMe)(3))(eta(5)-C(5)H(4)PPh(2))Re-PdCl(2) (4). IR spectroscopy reveals that both complexes possess a Re-Pd interaction which was confirmed by X-ray crystallography (Re-Pd bond distance = 2.762 A in and 2.774 A in ). Relativistic functional density theory calculations have also been carried out in order to probe the bonding in these compounds.

Synthesis, spectral, structural, second-order nonlinear optical properties and theoretical studies on new organometallic donor-acceptor substituted nickel(II) and copper(II) unsymmetrical Schiff-base complexes.

The synthesis, spectroscopic and structural characterization, linear and nonlinear optical properties, as well as the electrochemical behavior of a series of robust neutral binuclear M[Fc-C(O)CH=C(CH(3))N-X-N=CH-(2-O,5-R-C(6)H(3))] (M = Ni (4), Cu (5), X = o-C(6)H(4), R = H; M = Ni (9), X = CH(2)CH(2), R = OH), and their corresponding ionic trinuclear [M{Fc-C(O)CH=C(CH(3))N-X-N=CH-(eta(6)-2-O,5-R-C(6)H(3))RuCp*}][PF(6)] (6, 7, 10), M[ONNO]-type unsymmetrical Salophen and salen complexes featuring ferrocenyl (Fc) donor and the mixed sandwich acceptor [Cp*Ru(eta(6)- salicylidene)](+) as a push-pull moiety are reported in this paper (Fc = CpFe(eta(5)-C(5)H(4)); Cp = eta(5)-C(5)H(5); Cp* = eta(5)-C(5)Me(5)). The single-crystal X-ray structure of the bimetallic iron-nickel derivative 4 indicates a bowed structure of the unsymmetrical Schiff base skeleton. The Ni(II) ion is tetracoordinated in a square planar environment, with two nitrogen atoms and two oxygen atoms as donors. The new metalloligand [Fc-C(O)CH=C(CH(3))N(H)CH(2)CH(2)N=CH-(2,5-(OH)(2)C(6)H(3))] (8) obtained from the Schiff base condensation of 2,5-dihydroxobenzaldehyde with the half-unit precursor, Fc-C(O)CH=C(CH(3))N(H)CH(2)CH(2)NH(2) (2), is reported with its crystal structure showing partial delocalization of the heteroconjugated [O-C-C-C-N] frameworks with a dihedral angle between the respective planes of 60.76 degrees. Second order nonlinear optical (NLO) measurements were achieved using the Harmonic Light Scattering technique to probe the role of the M[ONNO] chromophores and of the pi-complexation of the salicylidene ring in the nonlinearity. All the complexes exhibit a second-order nonlinear response increasing with the nuclearity, the hyperpolarizability (beta) value of the trinuclear complex 10 being 1.5 time larger than that of the metalloligand 8 (beta = 155 x 10(-30) esu). A rationalization of the structural, electronic, and redox properties of the title compounds is provided, based on a theoretical investigation at the density functional theory (DFT) level. Their UV-visible spectra has been assigned with the help of time-dependent (TD) DFT calculations. They are dominated by LMCT, MLCT, and pi-pi* transitions.

Theoretical and electrochemical studies on organometallic symmetrical schiff base complexes of Zn(II), Cu(II), Ni(II) and Co(II).

The electronic communication between two redox centres through a Schiff base complex has been investigated in a series of ethylenediimine-bis(1-ferrocenyl-1,3-butanedionate) complexes of Zn(II) 1, Cu(II) 2, Ni(II) 3 and Co(II) 4. Cyclic voltammetry experiments of 1 and 2 exhibit a unique two-electron reversible oxidation wave, whereas in the case of 3 and 4 two and three one-electron oxidation processes are, respectively, observed. These results suggest some electronic interaction between the iron atoms of the ferrocenyl groups. DFT calculations carried out on model complexes show that for all the studied compounds the removal of the first two electrons corresponds to the oxidation processes of the iron centres in the weakly coupled ferrocenyl termini. The electronic communication between the two iron centres increases on going from 1 to 4. Finally, a re-indexation of the bands observed in the UV-Visible spectra has been carried out using TDDFT calculations.

Iron-molybdenum charge-transfer hybrids containing organometallic and inorganic fragments bridged by aryldiazenido ligands in a mu-eta(6):eta(1) coordination mode: syntheses, characterization, X-ray structures, electrochemistry, and theoretical investigation.

Representative members of a new family of covalently bonded charge-transfer molecular hybrids, of general formula [(eta5-C5H5)Fe(mu,eta6:eta1-p-RC6H4NN)Mo(eta2-S2CNEt2)3] +PF6- (R: H, 5+PF6-; Me, 6+PF6-; MeO, 7+PF6-) and [(eta5-C5Me5)Fe(mu,eta6:eta1-C6H5NN)Mo(eta2-S2CNEt2)3]+PF6-, 8+PF6-, have been synthesized by reaction of the corresponding mixed-sandwich organometallic hydrazines [(eta5-C5H5)Fe(eta6-p-RC6H4NHNH2)]+PF6- (R: H, 1+PF6-; Me, 2+PF6-; MeO, 3+PF6-) and [(eta5-C5Me5)Fe(eta6-C6H5NHNH2)]+PF6-, 4+PF6-, with cis-dioxomolybdenum(VI) bis(diethyldithiocarbamato) complex, [MoO2(S2CNEt2)2], in the presence of sodium diethyldithiocarbamato trihydrate, NaSC(=S)NEt2.3H2O, in refluxing methanol. These iron-molybdenum complexes consist of organometallic and inorganic fragments linked each other through a pi-conjugated aryldiazenido bridge coordinated in eta6 and eta1 modes, respectively. These complexes were fully characterized by FT-IR, UV-visible, and 1H NMR spectroscopies and, in the case of complex 7+PF6-, by single-crystal X-ray diffraction analysis. Likewise, the electrochemical and solvatochromic properties were studied by cyclic voltammetry and UV-visible spectroscopy, respectively. The electronic spectra of these hybrids show an absorption band in the 462-489 and 447-470 nm regions in CH2Cl2 and DMSO, respectively, indicating the existence of a charge-transfer transition from the inorganic donor to the organometallic acceptor fragments through the aryldiazenido spacer. A rationalization of the properties of 5+PF6--8+PF6- is provided through DFT calculations on a simplified model of 7+PF6-. Besides the heterodinuclear complexes 5+PF6--8+PF6-, the mononuclear molybdenum diazenido derivatives, [(eta1-p-RC6H4NN)Mo(eta2-S2CNEt2)3] (R: H, 9; Me, 10; MeO, 11), resulting from the decoordination of the [(eta5-C5H5)Fe]+ moiety of complexes 5+PF6--7+PF6-, were also isolated. For comparative studies, the crystalline and molecular structure of complex 10.Et2O was also determined by X-ray diffraction analysis and its electronic structure computed.