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1.
Chemistry ; 23(58): 14614-14622, 2017 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-28833778

RESUMO

Enzyme immobilization is of increasing importance for biocatalysis, for which good supports are critical. Herein, two new Preyssler-type polyoxometalate (POM)-based coordination polymers, namely, {[Cu(H2 biim)2 ][{Cu(H2 biim)2 (µ-H2 O)}2 Cu(H2 biim)(H2 O)2 ]H[({Cu(H2 biim)(H2 O)2 }0.5 )2 ((µ-C3 HN2 Cl2 ){Cu(H2 biim)}2 ){Z(H2 O)P5 W30 O110 }]⋅x H2 O}n (1: Z=Na, x=9; 2: Z=Ag, x=10; H2 biim=2,2'-biimidazole) were designed and synthesized. Compounds 1 and 2 exhibit the same skeletons, which contain multiple CuII complex fragments and penta-supported {ZP5 W30 } (Z=Na, Ag) clusters. They were first employed to immobilize horseradish peroxidase (HRP). Results show that compounds 1 and 2 are good supports for HRP immobilization, and exhibit higher enzyme loading, lower loading times, and excellent reusability. The immobilized HRP (HRP/1 or HRP/2) was further applied to detect H2 O2 , and good sensitivity, wide linear range, low detection limit, and fast response were achieved. This work shows that POM-based hybrid materials are a new kind of promising support for enzyme immobilization.


Assuntos
Peroxidase do Rábano Silvestre/química , Polímeros/química , Compostos de Tungstênio/química , Complexos de Coordenação/química , Cobre/química , Cristalografia por Raios X , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Peroxidase do Rábano Silvestre/metabolismo , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/metabolismo , Microscopia Confocal , Conformação Molecular , Termogravimetria
2.
Dalton Trans ; 53(24): 10226-10234, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38828535

RESUMO

In aqueous solution, a novel triangle-like tungstovanadate estertin derivative K10H10.5[(W4O15(H2O)2){(SnCH2CH2COO)2(V0.75W10.75/V0.25O39)}{{(SnCH2CH2COO)2(µ-OH)}2(SnCH2CH2COO)(VW10O37)}2]·31H2O ((SnR)8-V3W35, R = CH2CH2COO) was assembled by a conventional synthetic method. (SnR)8-V3W35 is composed of one [VW11O39]7- ({VW11}) and two [VW10O37]9- ({VW10}) units connected by eight [Sn(CH2)2COO]2+ groups and a {W4O19} cluster. Interestingly, there exists a pentagonal bipyramid WO7 polyhedral center surrounded by two SnCO5 and three WO6 octahedra, forming a pentagonal {(WO7)W3(SnR)2} cluster in this polyoxometalate (POM), which is also the first example of a pentagonal structure formed by transition metals (TMs) and main group organometals in the POM family. Furthermore, the structure of this organic-inorganic hybrid POM also exhibits the largest number of organotin groups introduced into the POM system. It was characterized with various physico-chemical and spectroscopic methods, including X-ray single crystal and powder diffraction analysis, 119Sn and 51V NMR, IR, thermal gravimetric analysis (TGA), etc. In addition, the catalytic activity of (SnR)8-V3W35 as a mimic of peroxidase was evaluated using o-phenylenediamine (OPD) as a peroxidase substrate. The major factors influencing the oxidation reaction such as pH, the dosage of (SnR)8-V3W35, and concentrations of OPD and H2O2 were mainly studied. (SnR)8-V3W35 exhibits good peroxidase-like catalytic activity. From another perspective, the successful acquisition of (SnR)8-V3W35 further proves the instability and easy reassembly characteristics of TM-sandwich-type tungstovanadates, which also provides a new assembly strategy for synthesizing POM-estertin derivatives.

3.
ACS Omega ; 7(5): 4429-4443, 2022 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-35155936

RESUMO

The development of acid-resistant and efficient corrosion inhibitors is of great significance for metal protection in many industrial processes. In this work, eight cases of sandwich-type polyoxometalate (POM)-based inorganic-organic hybrids, namely, carboxyethyltin and transition metal (TM) cofunctionalized tungstoantimonates and tungstobismuthates, formulated as Na x K10-x [(SnR)2(TM(H2O)3)2(B-ß-SbW9O33)2]·mH2O and Na y K10-y [(SnR)2(TM(H2O)3)2(B-ß-BiW9O33)2]·nH2O (abbreviated as SbW9-TM-SnR and BiW9-TM-SnR; TM = Mn, Co, Ni, and Zn; m = 18, 24, 24, and 22; n = 30, 25, 20, and 21; SnR = Sn(CH2CH2COO)) are first used as green corrosion inhibitors for 20# carbon steel in 0.5-2.0 M HCl solutions. Weight loss and electrochemical experiments prove that the corrosion inhibition efficiency is all above 81% for these POM-based corrosion inhibitors at 150 mg L-1, and SbW9-Mn-SnR shows the highest efficiency of 96.9% at 150 mg L-1 after immersion in a 0.5 M HCl solution for 10 h. Scanning electron microscopy-energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analyses show that these POM-based inhibitors form films on the carbon steel and the adsorption mechanism obeys the Langmuir adsorption model. The thermodynamic activation parameters were calculated, proving the occurrence of both chemical and physical adsorptions. The film-forming mechanism was also analyzed. This work provides guidance for synthesizing new lacunary POM-based materials to protect metals from corrosion in HCl pickling.

4.
Dalton Trans ; 50(42): 15198-15209, 2021 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-34622894

RESUMO

A new polyoxometalate (POM)-based organic-inorganic hybrid Cu-coordination polymer, namely {((Cu(bipy))2(µ-PhPO3)2Cu(bipy))2H(PCuW11O39)·3H2O}n (denoted as compound 1, bipy = 2,2'-bipyridine, PhPO3 = phenylphosphonate), was self-assembled hydrothermally. Single-crystal X-ray diffraction (SC-XRD) analysis shows that two unique types of 1D chains are present in compound 1, i.e. Cu(II)-organophosphine and organonitrogen complex cation ([((Cu(bipy))2(µ-PhPO3)2Cu(bipy))2]4+) chains and Cu-monosubstituted Keggin-type polyoxoanion ([PCuW11O39]5-) chains, forming a hetero-POM. Crystalline compound 1 as a new enzyme immobilization support exhibited a high horseradish peroxidase (HRP) loading capacity (268 mg g-1). The powder X-ray diffraction (PXRD), FTIR, zeta potential, confocal laser scanning microscopy (CLSM) and circular dichroism (CD) results show that HRP is only immobilized on the surface of compound 1 through simple physical adsorption without a secondary structure change. This POM-immobilized enzyme (HRP/1) was first used for degradation of pollutants in wastewater, and it showed a high degradation efficiency and TOC removal efficiency for phenol, 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) within 30 min reaction time. Moreover, HRP/1 exhibited better operational and storage stabilities and reusability compared with free HRP. This work suggests that POMs can be used as new supports for enzyme immobilization and POM-immobilized enzymes may be used as a new kind of biocatalyst for degradation of phenolic pollutants.


Assuntos
Peroxidase do Rábano Silvestre
5.
Dalton Trans ; 49(21): 7234-7244, 2020 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-32421129

RESUMO

Two new tungstosilicates (C(NH2)3)5KNa2H3[Sn(CH2CH2COOCH3)Co(H2O)2Si2W19O69]·10H2O (Si2W19-Co-SnRCOOCH3) and (C(NH2)3)5KNa2H3[Sn(CH2CH2COOCH3)Mn(H2O)2Si2W19O69]·13H2O (Si2W19-Mn-SnRCOOCH3) modified by organometal (OM) and transition metal (TM) ions were obtained, and they were self-assembled from mono-TM-containing (TM = Co, Mn) γ-[SiW10O35]6- (γ-SiW10)-based dimeric tungstosilicate and estertin Cl3SnCH2CH2COOCH3 in an acetate buffer solution, respectively. Their structures were determined with a series of physico-chemical and spectroscopic methods including X-ray crystallography, XRPD, etc. The estertin functional position in the tungstosilicate skeleton was analyzed by theoretical calculations using density functional theory (DFT). These two compounds have good catalytic activity for the oxidation of cyclohexanol to cyclohexanone. Meanwhile, they were composited with TiO2 using a facial layer-by-layer (LBL) method. The assembled composite films {Si2W19-TM-SnRCOOCH3/TiO2}n (TM = Co, Mn; n is the bilayer number, n = 1-6) exhibit efficient photoelectrocatalytic activity for the oxidation of methanol under irradiation of 100 mW cm-2 using a Xe lamp as a light source. And the {Si2W19-Co-SnRCOOCH3/TiO2}4 film produces the highest photocurrent among the composite films studied in this work. Combining the dark current measurement, surface photovoltage spectroscopy (SPV) and electrochemical impedance spectroscopy (EIS), the enhanced photoelectrocatalytic activity of {Si2W19-Co-SnRCOOCH3/TiO2}4 composite film for the oxidation of methanol is attributed to the suppressed electron-hole recombination, increased carrier separation efficiency and interfacial charge transfer.

6.
Dalton Trans ; 48(9): 2977-2987, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30742163

RESUMO

Carboxyethyltin and first-row transition metals (TMs) were firstly introduced into trivacant Keggin-type tungstoantimonate in an aqueous solution, leading to the formation of four crystalline organic-inorganic hybrid sandwich-type polyoxometalates (POMs), formulated as Na10-x-yKyHx[((TM)(H2O)3)2(Sn(CH2)2COO)2(SbW9O33)2]·nH2O (SbW9-TM-SnR, TM = Mn, Co, Ni, Zn; x = 1, 1, 0, 0; y = 0, 5, 5, 2; n = 18, 24, 24, 22, respectively). SbW9-TM-SnR exhibit high catalytic ability for the oxidation of cyclohexanol. Meanwhile, SbW9-TM-SnR were composited with polypyrrole (PPy) through an electropolymerization process, forming PPy-SbW9-TM-SnR, on which platinum (Pt) was further electro-deposited to prepare PPy-SbW9-TM-SnR/Pt for electrocatalytic methanol (CH3OH) oxidation in acid solution. The composition and morphology of PPy-SbW9-TM-SnR/Pt were determined by IR, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The electrochemical experimental results show that SbW9-TM-SnR and PPy obviously enhance the electrocatalytic and anti-intoxication abilities of Pt, and the highest peak current density of 0.87 mA cm-2, corresponding to 1.85 and 1.43 times higher than those of pure Pt and PPy/Pt electrodes respectively, is acquired for the PPy-SbW9-Ni-SnR/Pt composite electrode. These findings may enlarge the application of PPy and POMs in the electrocatalytic field.

7.
Toxicol In Vitro ; 22(4): 953-60, 2008 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-18359184

RESUMO

The epidemiological studies and recent data have provided convinced evidence that green tea and its major constituent epigallocatechin gallate (EGCG) might have the potential to lower the risk of cancers in humans. Metal ions, such as zinc and cadmium, which are necessary to our health, are important factors inducing many diseases including prostate cancer in the condition of absence or excess. EGCG can satisfactorily exhibit complex chemistry with metal ions because of multiple hydroxyl states, which in turn changes their bioactivities and metabolism pathways. This paper presents the results of an investigation of the cytotoxicity of EGCG against PC-3 prostate cancer cells in the presence and absence of Cd2+ in vitro. The results showed that both EGCG and Cd2+ suppressed viability and clonegenecity of PC-3 cells, and the suppression effect was enhanced when EGCG added with Cd2+. Although Cd2+ up-regulated the 67 kDa laminin receptor (67LR), which is a migration-associated protein, the cell migration ability was not significantly increased after each treatment. We also found that EGCG and Cd2+ directly interacted with mitochondrial, and the mixture of EGCG and Cd2+ (EGCG+Cd2+) significantly caused loss of the mitochondrial membrane potential, decrease of the ATP content and activation of caspase-9 compared with EGCG treated alone. Taken together, these findings suggest that Cd2+ enhanced the cytotoxicity of EGCG to PC-3 cells by up-regulating the 67LR and the mitochondria-mediated apoptosis pathway.


Assuntos
Anticarcinógenos/farmacologia , Apoptose/efeitos dos fármacos , Cádmio/farmacologia , Catequina/análogos & derivados , Regulação para Cima/efeitos dos fármacos , Trifosfato de Adenosina/metabolismo , Caspase 9/efeitos dos fármacos , Caspase 9/metabolismo , Catequina/farmacologia , Linhagem Celular Tumoral , Movimento Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Sinergismo Farmacológico , Humanos , Masculino , Potencial da Membrana Mitocondrial/efeitos dos fármacos , Neoplasias da Próstata/tratamento farmacológico , Neoplasias da Próstata/patologia , Receptores de Laminina/efeitos dos fármacos , Receptores de Laminina/metabolismo , Chá/química
8.
Acta Crystallogr Sect E Struct Rep Online ; 64(Pt 2): m308, 2008 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-21201281

RESUMO

There are independent cations and four chloride anions in the crystal structure of the title complex, [Co(C(6)H(6)N(4))(2)(H(2)O)(2)]Cl(2). In each cation, the Co(II) cation is coordinated by four N atoms from two biimidazole and two O atoms of two water mol-ecules; one Co atom is at a position of site symmetry m, the other at a position of site symmetry 2/m. All Cl(-) ions and water mol-ecules are also located on the mirror plane. Each structural unit is connected through O-H⋯Cl and N-H⋯Cl inter-molecular hydrogen bonds, forming a three-dimensional supramolecular structure.

9.
Acta Crystallogr Sect E Struct Rep Online ; 64(Pt 2): o534, 2008 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-21201553

RESUMO

The title compound, C(13)H(12)O(2)S(2), belonging to the group of dioxoketene cyclic S,S-acetals, was prepared from the corresponding dione in high yield. In the structure, the C=O and C=C bonds are not coplanar, with O=C-C=C torsion angles of -36.8 (4) and -21.0 (4)°. The dithian ring has a twisted conformation.

10.
Acta Crystallogr C Struct Chem ; 74(Pt 11): 1362-1369, 2018 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-30398189

RESUMO

The hydrothermal reaction of (NH4)3[CoMo6O24H6]·7H2O (CoMo6), CuCl2·2H2O and 2,2'-biimidazole (H2biim) led to the formation of a new coordination polymer, namely poly[diaquabis(2,2'-biimidazole)hexa-µ3-oxo-octa-µ2-oxo-hexaoxodicopper(II)hexamolybdate(VI)], [Cu2Mo6O20(C6H6N4)2(H2O)2]n (Cu-Mo6O20), at pH 2-3. It is obvious that in the formation of crystalline Cu-Mo6O20, the original Anderson-type skeleton of heteropolymolybdate CoMo6 was broken and the new isopolyhexamolybdate Mo6O20 unit was assembled. In Cu-Mo6O20, one Mo6O20 unit connects four [Cu(H2biim)(H2O)]2+ ions in a pentacoordinate mode via four terminal O atoms, resulting in a tetra-supported structure, and each CuII ion is shared by two adjacent Mo6O20 units. Infinite one-dimensional chains are established by linkage between two adjacent Mo6O20 units and two CuII ions, and these chains are further packed into a three-dimensional framework by hydrogen bonds, π-π interactions and electrostatic attractions. The catalytic performance of this crystalline material used as an efficient and reusable heterogeneous acid catalyst for carbonyl-group protection is discussed. In addition, Cu-Mo6O20 was applied as a new support for enzyme (horseradish peroxidase, HRP) immobilization, forming immobilized enzyme HRP/Cu-Mo6O20. HRP/Cu-Mo6O20 showed good catalytic activity and could be reused.


Assuntos
Complexos de Coordenação/química , Cobre/química , Enzimas Imobilizadas/química , Peroxidase do Rábano Silvestre/química , Imidazóis/química , Molibdênio/química , Ácidos/química , Armoracia/enzimologia , Catálise , Complexos de Coordenação/síntese química , Cristalografia por Raios X , Ligação de Hidrogênio , Ligantes , Estrutura Molecular
11.
Dalton Trans ; 47(39): 14060-14069, 2018 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-30238950

RESUMO

Three organic-inorganic hybrids containing Strandberg-type phenylphosphomolybdate anion [(C6H5PO3)2Mo5O15]4- with phenylphosphonate (PhP) centers, transition metal (TM) ions and 2,2'-biimidazole (H2biim) ligand, formulated as [(TM(H2biim)2)2(C6H5PO3)2Mo5O15]·H2O (TM = Co and Cu, abbreviated as Co-(PhP)2Mo5 and Cu-(PhP)2Mo5, respectively) and ([Ni(H2biim)3])2[(C6H5PO3)2Mo5O15]·2H2O (abbreviated as Ni-(PhP)2Mo5), were self-assembled by simple hydrothermal methods and were systematically characterized through single-crystal X-ray diffraction and other physicochemical and spectroscopic methods, which demonstrated that TM-H2biim complexes were firstly introduced into Strandberg-type organophosphomolybdate skeletons. Selecting the oxidation of cyclohexanol to cyclohexanone as a model reaction, using H2O2 as an oxidant, the catalytic oxidation activities of the Strandberg-type compounds were firstly evaluated. More importantly, these TM-(PhP)2Mo5 (TM = Co, Cu, Ni) compounds were employed to immobilize horseradish peroxidase (HRP), and showed high adsorption capacities for HRP. Laser scanning confocal microscope images showed that HRP adsorbed on the surfaces of the TM-(PhP)2Mo5 supports. Application of immobilized enzyme HRP/TM-(PhP)2Mo5 for the detection of H2O2 is also discussed.

12.
Dalton Trans ; 45(4): 1631-7, 2016 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-26690720

RESUMO

Using phenylphosphonic acid, simple tungstate and copper(ii) compounds as starting materials, an organic-inorganic hybrid Strandberg-type organophosphotungstate, {[(Cu(H2O)(µ-bipy))2(C6H5PO3)2W5O15]}n (bipy = 4,4'-bipyridyl) (1), was assembled successfully under hydrothermal conditions and characterized by physico-chemical and spectroscopic methods. Compound 1 represents the first example of a transition metal complex modified organophosphotungstate cluster. In the crystal structure of compound 1, the polymeric 1-D {Cu-bipy}n chains are interconnected by [(C6H5PO3)2W5O15](4-) (abbreviated as {(C6H5P)2W5}) units into a 3-D framework. A hollow Keggin isopolytungstate [H2W12O40](6-) ({W12})-Cu(ii) coordination polymer, {[Cu(bipy)2((µ-bipy)Cu(bipy))2(H2W12O40)]·12H2O}n (2), was obtained at different molar ratios of the starting materials and pH. The two Cu(ii) coordination polymers exhibit good acid-catalytic activity for the synthesis of cyclohexanone ethylene ketal. Their fluorescence properties were studied.

13.
ChemSusChem ; 9(10): 1125-33, 2016 05 23.
Artigo em Inglês | MEDLINE | ID: mdl-27098260

RESUMO

Two new carboxyethyltin-functionalized polyoxometalates (POMs) were successfully obtained and confirmed with physicochemical and spectroscopic methods including X-ray crystallography. The lowest unoccupied molecular orbitals of both compounds are higher in energy than that of TiO2 , and the optical band gaps of these compounds are smaller than that of TiO2 . Grafting them onto a TiO2 film created two kinds of novel photoanode materials that showed significantly enhanced photovoltaic and photocurrent responses, as well as improved photoelectrooxidation activities for methanol relative to that shown by a single TiO2 film. Further, P2 W15 -Co-SnR produced the largest photocurrent by exploring the photoelectric activities of a series of carboxyethyltin POM derivatives. This work provides new insight into the photoelectrochemical functionalization of POM-based organic-inorganic hybrids.


Assuntos
Processos Fotoquímicos , Titânio/química , Compostos de Tungstênio/química , Eletroquímica , Metanol/química , Modelos Moleculares , Conformação Molecular , Oxirredução , Temperatura
14.
ACS Appl Mater Interfaces ; 7(24): 13714-21, 2015 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-26030670

RESUMO

In the field of material chemistry, it is of great significance to develop abundant and sustainable materials for solar energy harvesting and management. Herein, after evaluating the energy band characteristics of 13 kinds of polyoxometalates (POMs), the trisubstituted POM compound K6H4[α-SiW9O37Co3(H2O)3]·17H2O (SiW9Co3) was first studied due to its relatively smaller band gap (2.23 eV) and higher lowest unoccupied molecular orbital (LUMO) level (-0.63 V vs NHE). Additionally, the preliminary computational modeling indicated that SiW9Co3 exhibited the donor-acceptor (D-A) structure, in which the cobalt oxygen clusters and tungsten skeletons act as the electron donor and electron acceptor, respectively. By employing SiW9Co3 to modify the TiO2 film, the visible photovoltaic and photocurrent response were both enhanced, and the light-induced photocurrent at 420 nm was improved by 7.1 times. Moreover, the highly dispersive and small sized SiW9Co3 nanoclusters loading on TiO2 were successfully achieved by fabricating the nanocomposite film of {TiO2/SiW9Co3}3 with the layer-by-layer method, which can result in the photovoltaic performance enhancement of dye-sensitized solar cells (DSSCs), of which the overall power conversion efficiency was improved by 25.6% from 6.79% to 8.53% through the synergistic effect of POMs and Ru-complex.

15.
Dalton Trans ; 44(14): 6423-30, 2015 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-25749136

RESUMO

A Dawson sandwich-type polyoxometalate {C(NH2)3}12H4[αßßα-{(Sn(C3H4O2))2Mn2(P2W15O56)2}]·22H2O (abbreviated as SnR-Mn-P2W15), functionalized by open chain carboxyethyltin groups, was first prepared in aqueous solution under conventional reaction conditions, and then structurally characterized by physicochemical and spectroscopic methods. Single crystal X-ray diffraction analysis revealed that two Mn(2+) cations and two [Sn(CH2CH2COO)](2+) groups are located in the internal and external positions in the so-called equatorial region of SnR-Mn-P2W15, respectively. Intriguingly, two exposed carboxyl groups act as stretching-arm brackets, which provide a favorable structure for potential further functionalization. The electrocatalytic activity of SnR-Mn-P2W15 towards the reduction of hydrogen peroxide and nitrite was studied. Additionally, its acid catalysis and oxidation catalysis activities in organic synthesis were investigated.


Assuntos
Compostos de Tungstênio/química , Compostos de Tungstênio/síntese química , Catálise , Técnicas de Química Sintética , Cicloexanóis/química , Cicloexanonas/química , Peróxido de Hidrogênio/química , Modelos Moleculares , Conformação Molecular , Nitritos/química , Oxirredução
16.
Dalton Trans ; 43(45): 17172-6, 2014 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-25317986

RESUMO

Two novel Strandberg-type organophosphomolybdate hybrid compounds [(Cu(H2O))2(µ-bipy)2(C6H5PO3)2Mo5O15]n (1) and [(Cu(H2O)2)2(µ-bipy)(C6H5PO3)2Mo5O15]n (2) (bipy = 4,4'-bipyridyl) were prepared under mild hydrothermal conditions and structurally characterized by physico-chemical and spectroscopic methods. Single crystal X-ray diffraction analysis reveals that compounds 1 and 2 are polyoxometalate-based Cu-coordination polymers with a three-dimensional framework. In 1, the Cu(2+) ions not only link [(C6H5PO3)2Mo5O15](4-) (abbreviated as {(C6H5P)2Mo5}) polyanions, but also act as connectors of bipy ligands to produce two symmetrical 1-D chains, all 1-D chains are further held together by polyanions to generate a 3-D network. In 2, each {(C6H5P)2Mo5} polyanion acting as a hexadentate ligand links four Cu(II)-bipy/H2O units, forming 2-D plane structures, which are further bridged by Cu(II)-bipy-Cu(II) fragments to generate a 3-D network. Their fluorescence properties and catalytic properties for the synthesis of cyclohexanone ethylene ketal were also investigated.

17.
Dalton Trans ; 43(15): 5840-6, 2014 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-24577152

RESUMO

Three new inorganic-organic hybrid compounds based on Strandberg-type anions and Zn(ii)-H2biim/H2O subunits, namely {H4(H2biim)3}[Zn(H2biim)(H3biim)(H2O)(HP2Mo5O23)]2·3H2O (1), {H9(H2biim)7}[(µ-biim){(Zn(H2O)2)0.5(HP2Mo5O23)}2]·7H2O (2) and {H7(H2biim)7}[Zn(H2biim)(H2O)2(HP2Mo5O23)][H2P2Mo5O23]·8H2O (3) (H2biim = 2,2'-biimidazole), have been synthesized in aqueous solutions and characterized. They were also used as efficient and reusable catalysts for the protection of carbonyl compounds. Their fascinating structural features are that mono Zn(ii)-supporting biphosphopentamolybdate ({P2Mo5}) clusters exist in their crystal structures, and the nitrogen donor ligand H2biim exhibits three different coordination modes in these three compounds, respectively: for 1, two 2,2'-biimidazole molecules, as mono- and bidentate ligands coordinate to the same Zn(ii) ion; for 2, one bi-negative tetradentate ligand µ-biim bridges two Zn(ii) ions, while for 3, one neutral bidentate H2biim ligand links one Zn(ii) ion. Most importantly, compounds 1-3 represent the first example where Strandberg-type POMs are used as acid-catalysts in an organic reaction.

18.
Chem Commun (Camb) ; 50(93): 14678-81, 2014 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-25317838

RESUMO

Two novel open-chain carboxyethyltin decorated sandwich-type germanotungstates have been successfully synthesized. They could markedly increase the electrocatalytic activity of single-walled carbon nanotubes toward triiodide reduction when assembled into composite electrodes, which have shown a conversion efficiency of 6.32% that is comparable to that of Pt electrodes (6.29%) when used as counter electrodes in dye-sensitized solar cells.

19.
Dalton Trans ; 39(14): 3369-71, 2010 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-20379527

RESUMO

The reaction of Cl(3)Sn(CH(2))(2)COOCH(3), [H(2)P(2)W(12)O(48)](12-) and WO(4)(2-) in acetate buffer solution led to the hydrolysis of estertin into a carboxyethyltin group and the assembly of a new tetra(organotin)-decorated boat-like polyoxometalate.

20.
Eur J Pharmacol ; 616(1-3): 251-5, 2009 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-19577562

RESUMO

The laminin tyrosine-isoleucine-glycine-serine-arginine (YIGSR) peptide, corresponding to the 929-933 sequence of beta1 chain, is known to inhibit tumor growth and metastasis. In the present study, we observed that YIGSR not only inhibited the growth and migration of prostate cancer cells in a dose-dependent manner but also decreased mitochondrial membrane potential, inhibited ATP synthesis and increased caspase-9 activity. Investigation into the interaction of YIGSR with 67LR, the receptor for laminin and polyphenol (-) epigallocatechin-3-gallate (EGCG) employing MVD (Molegro Virtual Docker, an integrated platform for predicting protein ligand interactions), revealed that the binding site of YIGSR was the same as that of EGCG that explains as to why YIGSR is able to inhibit the cytotoxicity of EGCG against PC-3 cells.


Assuntos
Laminina/química , Oligopeptídeos/química , Oligopeptídeos/farmacologia , Neoplasias da Próstata/patologia , Trifosfato de Adenosina/metabolismo , Sequência de Aminoácidos , Androgênios/farmacologia , Caspase 9/metabolismo , Catequina/análogos & derivados , Catequina/metabolismo , Catequina/farmacologia , Linhagem Celular Tumoral , Movimento Celular/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Humanos , Masculino , Potencial da Membrana Mitocondrial/efeitos dos fármacos , Modelos Moleculares , Conformação Molecular , Oligopeptídeos/metabolismo , Receptores de Laminina/metabolismo
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