RESUMO
BACKGROUND: 2(3H)-Benzoxazolone derivatives are preferential structural blocks in pharmacological probe designing with the possibility of modifications at various positions on the core structure. Benzoxazolones showed various biological activities such as analgesics, anti-inflammatory and anti-cancer. OBJECTIVE: In the present work, we have prepared new Mannich bases of 2(3H)-benzoxazolone derivatives and evaluated their cytotoxicities and proapoptotic properties in MCF-7 breast cancer cell line. METHODS: The structures of these compounds were characterized by FT-IR, elemental analysis, 1H and 13C NMR. Cytotoxicities of all the target compounds were investigated by MTT assay. Apoptotic properties of compounds were evaluated by immunocytochemistry using antibodies against caspase-3, cytochrome-c, FasL, and also TUNEL assay. RESULTS: These two novel compounds, 1 and 2, both have the same piperazine substituent on the nitrogen atom of benzoxazolone and the main difference in the structures of these compounds is the presence of Cl substituent at the 5- position of the benzoxazolone ring. MTT results showed that compounds 1 and 2 were effective in terms of reduction of cell viability at 100µM and 50µM concentration for 48h, respectively. As a result of immunohistochemical staining, Fas L and caspase-3 immunoreactivities were significantly increased in MCF-7 cells after treatment with compound 1. Additionally, caspase-3 and cytochrome-c immunoreactivities were also increased significantly in MCF-7 cells after treatment with compound 2. The number of TUNEL positive cells was significantly higher in MCF-7 cells when compared with the control group after treatment with both compounds 1 and 2. CONCLUSION: It could be concluded that N-substituted benzoxazolone derivatives increase potential anti-cancer effects and they could be promising novel therapeutic agents for chemotherapy.
Assuntos
Antineoplásicos/síntese química , Benzoxazóis/síntese química , Neoplasias da Mama/tratamento farmacológico , Analgésicos/farmacologia , Anti-Inflamatórios/farmacologia , Antineoplásicos/farmacologia , Apoptose/efeitos dos fármacos , Benzoxazóis/farmacologia , Caspase 3/metabolismo , Ensaios de Seleção de Medicamentos Antitumorais , Complexo IV da Cadeia de Transporte de Elétrons/metabolismo , Proteína Ligante Fas/metabolismo , Humanos , Células MCF-7 , Piperazina/química , Relação Estrutura-AtividadeRESUMO
Sn94- reacts with Pt(PPh3)4 in ethylenediamine/toluene solvent mixtures in the presence of 2,2,2-cryptand to give four different complexes: "Rudolph's complex" of proposed formula [Sn9Pt(PPh3)x]4- (2), the previously reported [Pt@Sn9Pt(PPh3)]2- ion (3), and the title complexes Pt2@Sn174- (4) and Pt@Sn9H3- (5). The use of Pt(norbornene)3 instead of Pt(PPh3)4 gives complex 4 exclusively. The structure of 4 contains two Pt atoms centered in a capsule-shaped Sn17 cage. The complex is highly dynamic in solution showing single, mutually coupled 119Sn and 195Pt NMR resonances indicative of an intramolecular liquidlike dynamic exchange process. Complex 5 has been characterized by selectively decoupled 1H, 119Sn, and 195Pt NMR experiments and shows similar liquidlike fluxionality. In addition, the H atom scrambles across the cage showing small couplings to both Sn and Pt atoms. Neither 3 nor 4 obeys Wades rules; they adopt structures more akin to the subunits in alloys such as PtSn4. The structural and chemical relevance to supported PtSn4 heterogeneous catalysts is discussed.
Assuntos
Compostos de Platina/síntese química , Compostos de Estanho/síntese química , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Conformação Molecular , Compostos de Platina/química , Compostos de Estanho/químicaRESUMO
Recyclable and reusable mesoporous silica anchored Ru catalysts based on 4,4'-substituted BINAPs were synthesized and used for the hydrogenation of beta-alkyl beta-ketoesters with up to 98.6% e.e. and beta-aryl beta-ketoesters with up to 95.2% e.e.
RESUMO
Toluene solutions of Nb(toluene)(2) react with ethylenediamine solutions of K(3)E(7) (E = As, Sb) in the presence of 2,2,2-crypt to give [NbAs(8)](3-) (2) and [NbSb(8)](3-) (3) ions, respectively, in low yields. The (133)Cs NMR spectroscopy, ESIMS results (negative ion mode), and single-crystal X-ray structures of the ions are reported. The complexes have S(8)-like E(8) rings with Nb atoms in the center. The 1:1 complex of 2 with Cs+ was observed in solution and also in the gas phase as the oxidized ion [CsNbAs(8)](1-). The anion 2 selectively binds to Cs(+) in solution even in the presence of excess Na(+). Other gas-phase ions formed include [Cs(2)(NbAs(8))](1-), [KCs(NbAs(8))](1-), [KCs(NbAs(8))(2)](1-), [KNbAs(8)](1-), and [K(2)NbAs(8)](1-).
RESUMO
The [ME(8)](n)()(-) ions where M = Cr, Mo; E = As, Sb; n = 2, 3 have been prepared from the corresponding E(7)(3)(-) Zintl ions and M(naphthalene)(2) precursors. The complexes and their [A(crypt)](+) salts (A = Na, K) are formed in 20-45% crystalline yields and have been characterized by UV-vis spectroscopy, EPR, cyclic voltammetry, magnetic susceptibility, electrospray mass spectrometry (ESI-MS) and single-crystal X-ray diffraction. The structures are defined by crown-like cyclo-E(8) rings that are centered by transition metals. MoAs(8)(2)(-) (2) is a 16 e(-) diamagnetic complex whereas MoSb(8)(3)(-) (5) and the CrAs(8)(3)(-) salts (3 and 4) are 17 e(-) paramagnetic complexes. The ESI-MS spectra show free and alkali-complexed ME(8)(n)()(-) ions. The K(+) salt of CrAs(8)(3)(-) (4) crystallizes in a one-dimensional chain structure of [KCrAs(8)](2)(-) repeat units whereas the Na(+) salt (3) as well as 2 and 5 crystallize in "free ion" structures. The Cr atoms in 3 and 4 are formally d(1) Cr(5+) centers that show EPR signals at g = 2.001 with small As hyperfine interactions of 3.6 G. The susceptibility of the [KCrAs(8)](2)(-) salt 4 was modeled as a 1D Heisenberg antiferromagnet with a small -J/k(B) of 3K arising from antiferromagnetic couplings of the d(1) centers whereas 3 shows Curie-Weiss behavior. The electrochemical studies show metal-based oxidations for 3-5 but a ligand based oxidation for 2. The electronic spectra are interpreted in terms of the molecular orbital analysis of Li and Wu. The differences in formal oxidation states of the metals is described in terms of a Zintl-Klemm formalism involving E(8)(8)(-) rings that are isoelectronic to S(8). The factors governing the formation of 1D chains versus free ions are presented.
RESUMO
[Sn(9)Pt(2)(PPh(3))](2)(-) (2) was prepared from Pt(PPh(3))(4), K(4)Sn(9), and 2,2,2-cryptand in en/toluene solvent mixtures. The [K(2,2,2-cryptand)](+) salt is very air and moisture sensitive and has been characterized by ESI-MS, variable-temperature (119)Sn, (31)P, and (195)Pt NMR and single-crystal X-ray diffraction studies. The structure of 2 comprises an elongated tricapped Sn(9) trigonal prism with a capping PtPPh(3), an interstitial Pt atom, a hypercloso electron count (10 vertex, 20 electron) and C(3)(v)() point symmetry. Hydrogenation trapping experiments and deuterium labeling studies showed that the formation of 2 involves a double C-H activation of solvent molecules (en or DMSO) with the elimination of H(2) gas. The ESI-MS analysis of 2 showed the K[Sn(9)Pt(2)(PPh(3))](1)(-) parent ion, an oxidized [Sn(9)Pt(2)(PPh(3))](1)(-) ion, and the protonated binary cluster anion [HSn(9)Pt(2)](1)(-). 2 is highly fluxional in solution giving rise to a single time-averaged (119)Sn NMR signal for all nine Sn atoms but the Pt atoms remain distinct. The exchange is intramolecular and is consistent with a rigid, linear Pt-Pt-PPh(3) rod embedded in a liquidlike Sn(9) matrix. [Sn(9)Ni(2)(CO)](3)(-) (3) was prepared from Ni(CO)(2)(PPh(3))(2), K(4)Sn(9), and 2,2,2-cryptand in en/toluene solvent mixtures. The [K(2,2,2-cryptand)](+) salt is very air and moisture sensitive, is paramagnetic, and has been characterized by ESI-MS, EPR, and single-crystal X-ray diffraction. Complex 3 is a 10-vertex 21-electron polyhedron, a slightly distorted closo-Sn(9)Ni cluster with an additional interstitial Ni atom and overall C(4)(v)() point symmetry. The EPR spectrum showed a five-line pattern due to 4.8-G hyperfine interactions involving all nine tin atoms. The ESI-MS analysis showed weak signals for the potassium complex [K(2)Sn(9)Ni(2)(CO)](1-) and the ligand-free binary ions [K(2)Sn(9)Ni(2)](1)(-), [KSn(9)Ni(2)](1)(-), and [HSn(9)Ni(2)](1)(-).
RESUMO
Sitting in a tin chair: the compound [Nb(η-C6 H5 Me)2 ] reacts with the Sn94- ion in ethylenediamine to give the [(η-C6 H5 Me)NbSn6 Nb(η-C6 H5 Me)]2- ion, 1. The complex contains a new Zintl ion, Sn612- , with a chair cyclohexane-like structure and 2c-2e bonds.