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1.
Artículo en Inglés | MEDLINE | ID: mdl-39256276

RESUMEN

INTRODUCTION: Lateral unicompartmental knee arthroplasties (LUKA) account for only < 1% of all knee arthroplasties and for only 5-10% of all unicompartmental knee replacements. This means that there is less published literature on these procedures and that the surgeon's experience with them is smaller than with medial UKA. The aim of this study was to analyze the survival and the clinical-functional outcomes of LUKA according to the type of bearing surface (all-polyethylene versus metal-backed) used. MATERIALS AND METHODS: This was a retrospective study including 42 LUKAs operated between 2009 and 2021. Two fixed polyethylene-bearing models were used: the all-polyethylene ACCURIS knee (38%) and the metal-backed Triathlon PKR system (62%). Demographic parameters, knee range of motion (ROM), tibiofemoral alignment, implant survival (as estimated with the Kaplan-Meier curve), and clinical-functional outcomes (as measured with the Knee Society Score) were analyzed. RESULTS: Average patient age was 65.5 (range, 36-87) years and mean follow-up was 8.2 (range, 2.1-12.8) years. Thirty LUKAs (71.4%) were implanted in women. The main reason for performing a LUKA was osteoarthritis (88.1%). No patient developed post-surgical complications or had to be re-operated. Overall LUKA survival was 100% at 1-year and 5-year's follow-up. Knee Society Score, knee ROM and tibiofemoral alignment all improved significantly post-surgery (p < 0.001). The clinical Knee Society Score increased from 46.5 ± 14.5 pre-surgery to 93.5 ± 10.3 post-surgery, the functional Knee Society Score increased from 48.1 ± 13.5 pre-surgery to 94.6 ± 9.3 post-surgery, maximum flexion increased from 108.5 ± 8.7 degrees pre-surgery to 121 ± 8.9 degrees post-surgery and tibiofemoral alignment was corrected from 13.1 ± 1.74 degrees pre-surgery to 5.7 ± 0.8 degrees post-surgery. There were no statistically significant clinical-functional improvement or knee ROM differences between groups (p < 0.05, respectively). CONCLUSION: LUKA is a valid and definitive option for patients with lateral tibiofemoral osteoarthritis, with a survival rate of > 95% at 5-years follow-up. Clinical-functional outcomes are the same, irrespective of the tibial component used.

2.
Arch Orthop Trauma Surg ; 144(1): 347-355, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37743356

RESUMEN

INTRODUCTION: Few information has been published on the survival of unicompartmental knee arthroplasty (UKA) and fixed-bearing tibial components. The aim of this study is to analyze if UKA survival varies according to UKA model used and to analyze the possible risk factors for UKA revision. MATERIALS AND METHODS: A retrospective study analyzing 301 UKAs (ACCURIS, all-polyethylene tibial component, 152; Triathlon PKR, metal-backed tibial component, 149) was performed. Demographic parameters as well as implant survival and cause of prosthetic revision were analyzed. The Kaplan-Meier survival analysis, the log-rank test and the Cox multiple regression were used for the analysis. RESULTS: Average follow-up was 8.1 ± 3.08-years. Average age was 68.1 ± 8.6-years; 70.4% of subjects were women. The ACCURIS UKA group had a UKA revision rate higher compared to the Triathlon PKR group (16/152, 10.6% vs 5/149, 3.4%, respectively; p < 0.001). The main cause of prosthetic revision was aseptic loosening (5/21, 23.8%). All aseptic loosening cases and tibial component collapse were reported with the ACCURIS UKA group. Overall UKA survival was 98.01% (95% CI 95.62-99.1) at 1-year, 94.27% (95% CI 90.95-96.4) at 5-years and 92.38% (95% CI 88.48-94.99) at 10-years' follow-up. There were no differences in the Kaplan-Meier survival curves regarding operated side or affected tibiofemoral compartment (log-rank test = 0.614 and 0.763, respectively). However, Kaplan-Meier survival curve according to UKA model used was different (log-rank test = 0.033). The metal-backed component appeared to be a protector factor for UKA revision when adjusted for age, sex, operated side, and affected tibiofemoral compartment (Hazard Ratio 0.32, p = 0.031). CONCLUSION: Fixed-bearing UKAs showed excellent mid- and long-term survival rates. Aseptic loosening is the main cause of implant failure. PKR group (metal-backed component) seem to be a protector factor to UKA revision when it was compared with ACCURIS UKA group (all-polyethylene tibial component).


Asunto(s)
Artroplastia de Reemplazo de Rodilla , Prótesis de la Rodilla , Osteoartritis de la Rodilla , Humanos , Femenino , Persona de Mediana Edad , Anciano , Masculino , Artroplastia de Reemplazo de Rodilla/efectos adversos , Prótesis de la Rodilla/efectos adversos , Estudios Retrospectivos , Reoperación/efectos adversos , Falla de Prótesis , Polietileno , Metales , Osteoartritis de la Rodilla/cirugía , Resultado del Tratamiento , Articulación de la Rodilla/cirugía
3.
Eur J Orthop Surg Traumatol ; 34(2): 1183-1192, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38006463

RESUMEN

PURPOSE: To determine the survival and patient-reported outcomes in non-oncological patients treated with proximal femoral resection (PFR) using MEG for femoral reconstruction. MATERIALS AND METHODS: This retrospective study included 16 patients. Demographic variables and complications developed were analyzed. Clinical-functional outcomes were measured using the modified Harris score (mHSS), numeric Pain Rating Scale (NPRS) and Musculoskeletal Tumor Society (MSTS) score. MEG survival was estimated using a Kaplan-Meier survival analysis. RESULTS: Average follow-up was 5 years (range, 1-9). The 75% of patients were overweight and women with an average age of 74.2 ± 5.9-years (BMI of 28.5 ± 4.2 kg/m2). The main cause of MEG was periprosthetic infection (43.7%). The 50% of patients had post-surgical complications regarding with MEG, being the most frequent seromas and MEG dislocation. Implant survival was 93.4% and 80.9% at 3 and 7 years of follow-up, respectively. The functional results at the end of the follow-up with respect to the pre-surgical state improved from 9.5 ± 2.6 to 3 ± 0.9 mean NPRS and 26.5 ± 6.8 to 69.5 ± 13.5 mean mHHS, p < 0.001, respectively. The mean MSTS score was 68.1% that these results were considered excellent. CONCLUSIONS: The MEG for reconstruct III-IV femoral defects is a good therapeutic option that offers an acceptable clinical-functional result. Short-term and medium-term survival was greater than 80%. The most frequent complications are seromas and MEG dislocation. The use of constrained liner and abductor system reconstruction is essential to prevent the dislocation.


Asunto(s)
Artroplastia de Reemplazo de Cadera , Prótesis de Cadera , Humanos , Femenino , Anciano , Anciano de 80 o más Años , Diseño de Prótesis , Estudios de Seguimiento , Estudios Retrospectivos , Seroma/patología , Seroma/cirugía , Resultado del Tratamiento , Falla de Prótesis , Fémur/patología , Reoperación , Artroplastia de Reemplazo de Cadera/métodos
4.
Molecules ; 28(19)2023 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-37836688

RESUMEN

The sol-gel method is a straightforward technique that allows electrode modification with silica thin films. Furthermore, the silica pores could be functionalized to enhance the electrical conductivity and reactivity of the silica films. In this context, silica thin films were functionalized with ferrocene species. This functionalization was performed by electroassisted accumulation, generating a micro-structured composite electrode (Fc@SiO2 electrode). These modified electrodes were characterized by electrochemical and spectroelectrochemical methods, pointing out that ferrocene species were confined with high stability within the microporous silica thin film, demonstrating the good adsorption capacity of the silica. While the spectroelectrochemical characterization indicates that only a fraction of the confined species within the silica films were electroactive, the electrochemical results demonstrate that the Fc@SiO2 film enhances the electrochemical response of cytochrome c in a solution, which gives rise to further applications of these films for redox-controlled release and electrochemical detection of other redox-active proteins.

5.
Biosensors (Basel) ; 13(3)2023 Mar 21.
Artículo en Inglés | MEDLINE | ID: mdl-36979620

RESUMEN

This work describes the development and characterization of fluorescent nanocomposite hydrogels, with high swelling and absorption capacity, and prepared using a green protocol. These fluorescent materials are obtained by incorporating, for the first time, polyfluorenes-based nanoparticles with different emission bands-poly[9,9-dioctylfluorenyl-2,7-diyl] (PFO) and poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(1,4-benzo-{2,1,3}-thiadiazole)] (F8BT)-into a three-dimensional polymeric network based on polyacrylamide. To this end, two strategies were explored: incorporation of the nanoparticles during the polymerization process (in situ) and embedment after the hydrogel formation (ex situ). The results show that the combination of PFO nanoparticles introduced by the ex situ method provided materials with good storage stability, homogeneity and reproducibility properties, allowing their preservation in the form of xerogel. The fluorescent nanocomposite hydrogels have been tested as a transportable and user-friendly sensing platform. In particular, the ability of these materials to specifically detect the enzyme alkaline phosphatase (ALP) has been evaluated as a proof-of-concept. The sensor was able to quantify the presence of the enzyme in an aqueous sample with a response time of 10 min and LOD of 21 nM. Given these results, we consider that this device shows great potential for quantifying physiological ALP levels as well as enzyme activity in environmental samples.


Asunto(s)
Nanopartículas , Polímeros , Nanogeles , Fosfatasa Alcalina , Reproducibilidad de los Resultados , Hidrogeles
6.
Biosensors (Basel) ; 12(9)2022 Aug 29.
Artículo en Inglés | MEDLINE | ID: mdl-36140083

RESUMEN

The present work describes the development of an easy-to-use portable electrochemical biosensor based on alkaline phosphatase (ALP) as a recognition element, which has been immobilized in acrylamide-based hydrogels prepared through a green protocol over disposable screen-printed electrodes. To carry out the electrochemical transduction, an electroinactive substrate (hydroquinone diphosphate) was used in the presence of the enzyme and then it was hydrolyzed to an electroactive species (hydroquinone). The activity of the protein within the matrix was determined voltammetrically. Due to the adhesive properties of the hydrogel, this was easily deposited on the surface of the electrodes, greatly increasing the sensitivity of the biosensor. The device was optimized to allow the determination of phosphate ion, a competitive inhibitor of ALP, in aqueous media. Our study provides a proof-of-concept demonstrating the potential use of the developed biosensor for in situ, real-time measurement of water pollutants that act as ALP inhibitors.


Asunto(s)
Técnicas Biosensibles , Contaminantes del Agua , Acrilamida , Fosfatasa Alcalina , Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos , Electrodos , Hidrogeles , Hidroquinonas , Fosfatos
7.
J Inorg Biochem ; 235: 111924, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35841721

RESUMEN

Complexes Na3[Ag(NHCR)2], 2a-e and 2b'-c', where NHCR is a N-heterocyclic carbene of the 2,2'-(1H-2λ3,3λ4-imidazole-1,3-diyl)dicarboxylate type, were prepared by treatment of compounds HLR, 1a-e and 1b'-c' (2-(1-(carboxyalkyl)-1H-imidazol-3-ium-3-yl)carboxylate), with silver oxide in the presence of aqueous sodium hydroxide. They were characterized by analytical, spectroscopic (infrared, IR, 1H and 13C nuclear magnetic resonance, NMR, and circular dichroism) and X-ray methods (2a). In the solid state, the anionic part of complex 2a, [Ag(NHCH)2]3-, shows a linear disposition of Ccarbene-Ag-Ccarbene atoms and an eclipsed conformation of the two NHC ligands. The proposed bis(NHC) nature of the silver complexes was maintained in solution according to NMR and density functional theory (DFT) calculations. The cytotoxic activity of compounds 2 was evaluated against four cancer cell lines and one non-cancerous cell line and several structure-activity correlations were found for these complexes. For instance, the activity decreased when the bulkiness of the R alkyl group in Na3[Ag(NHCR)2] increased. More interesting is the detected chirality-anticancer relationship, where complexes Na3[Ag{(S,S)-NHCR}2] (R = Me, 2b; iPr, 2c) showed better anticancer activity than those of their enantiomeric derivatives Na3[Ag{(R,R)-NHCR}2] (R = Me, 2b'; iPr, 2c').


Asunto(s)
Antineoplásicos , Compuestos Heterocíclicos , Antineoplásicos/química , Antineoplásicos/farmacología , Cristalografía por Rayos X , Compuestos Heterocíclicos/química , Compuestos Heterocíclicos/farmacología , Metano/análogos & derivados , Estructura Molecular
8.
Pharmaceutics ; 14(4)2022 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-35456582

RESUMEN

Complexes {Ag[NHCMes,R]}n (R = H, 2a; Me, 2b and 2b'; iPr, 2c; iBu, 2d), were prepared by treatment of imidazolium precursor compounds [ImMes,R] (2-(3-mesityl-1H-imidazol-3-ium-1-yl)acetate, 1a, (S)-2-alkyl(3-mesityl-1H-imidazol-3-ium-1-yl)acetate, 1b-d, and (R)-2-methyl(3-mesityl-1H-imidazol-3-ium-1-yl)acetate, 1b', with Ag2O under appropriate conditions. They were characterised by analytical, spectroscopic (IR, 1H, and 13C NMR and polarimetry), and X-ray methods (2a). In the solid state, 2a is a one-dimensional coordination polymer, in which the silver(I) cation is bonded to the carbene ligand and to the carboxylate group of a symmetry-related Ag[NHCMes,H] moiety. The coordination environment of the silver centre is well described by the DFT study of the dimeric model {Ag[NHCMes,H]}2. The antimicrobial properties of these complexes were evaluated versus Gram-negative bacteria E. coli and P. aeruginosa. From the observed MIC and MBC values (minimal inhibitory concentration and minimal bactericidal concentration, respectively), complex 2b' showed the best antimicrobial properties (eutomer), which were significantly better than those of its enantiomeric derivative 2b (distomer). Additionally, analysis of MIC and MBC values of 2a-d reveal a clear structure-antimicrobial effect relationship. Antimicrobial activity decreases when the steric properties of the R alkyl group in {Ag[NHCMes,R]}n increase.

9.
Dalton Trans ; 51(13): 5061-5071, 2022 Mar 29.
Artículo en Inglés | MEDLINE | ID: mdl-35294509

RESUMEN

Complexes [Ag(LR)], 2 (LR = 2,2'-(imidazolium-1,3-diyl)di(2-alkylacetate)), were prepared by treatment of compounds HLR, 1, with Ag2O. They were characterised by analytical, spectroscopic (IR, 1H and 13C NMR and polarimetry) and X-ray methods (2c, 2c' and 2e). In the solid state, these compounds are novel one-dimensional or two-dimensional coordination polymers in which silver(I) cations are connected via the chiral [LR]- anion with unprecedented coordination modes. The antimicrobial properties of these complexes were evaluated. 2a and 2b' showed the best antimicrobial properties (minimal inhibitory concentrations and minimal bactericidal concentration) for Pseudomonas aeruginosa and Escherichia coli pathogens. Eutomers 2b' and 2c' showed slightly better antimicrobial properties than their respective enantiomers 2b and 2c.


Asunto(s)
Antiinfecciosos , Plata , Antibacterianos/química , Antibacterianos/farmacología , Antiinfecciosos/química , Antiinfecciosos/farmacología , Ácidos Carboxílicos/química , Pruebas de Sensibilidad Microbiana , Plata/química , Plata/farmacología
10.
Materials (Basel) ; 13(5)2020 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-32155965

RESUMEN

Hybrid silica-modified materials were synthesized on glassy carbon (GC) electrodes by electroassisted deposition of sol-gel precursors. Single-wall carbon nanotubes (SWCNTs) were dispersed in a silica matrix (SWCNT@SiO2) to enhance the electrochemical performance of an inorganic matrix. The electrochemical behavior of the composite electrodes was tested against the ferrocene redox probe. The SWCNT@SiO2 presents an improvement in the electrochemical performance towards ferrocene. The heterogeneous rate constant of the SWCNT@SiO2 can be enhanced by the insertion of poly(3,4-Ethylendioxythiophene)-poly(sodium 4-styrenesulfonate) PEDOT-PSS within the silica matrix, and this composite was synthesized successfully by reactive electrochemical polymerization of the precursor EDOT in aqueous solution. The SWCNT@SiO2-PEDOT-PSS composite electrodes showed a heterogeneous rate constant more than three times higher than the electrode without conducting polymer. Similarly, the electroactive area was also enhanced to more than twice the area of SWCNT@SiO2-modified electrodes. The morphology of the sample films was analyzed by scanning electron microscopy (SEM).

11.
Dalton Trans ; 48(24): 8731-8739, 2019 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-31139785

RESUMEN

Chiral Na[(S)-LR] (R = Me, 1a; iPr, 1b; CH2iPr, 1c, and (S)-secBu, 1d) and Na[(R)-LR] (R = Me, 1a') compounds were synthesised following standard procedures. New compounds 1d and 1a' were analytically and spectroscopically characterised. 1a and 1c were structurally identified by single-crystal X-ray diffraction methods as homochiral 2D coordination polymers, {Na(H2O)[(S)-LMe]}n and {Na[(S)-LCH2iPr]}n, respectively. Both (S)-2alkyl,2-(1H-imidazol-1-yl)acetate anions displayed unprecedented coordination modes in these coordination polymers: µ3κ2OκO' for 1a and µ4κ2Oκ2O' for 1c. Enantiomeric species 1a', {Na(H2O)[(R)-LMe]}n, showed the same X-ray powder diffractogram (XRPD) as 1a, in agreement with a similar crystal structure. DFT calculations on the [LR]- anions confirmed their coordination capabilities as ditopic linkers. In fact, the reaction of Na[LR] with several metal salts yielded the following coordination polymers: {Ag[(S)-LMe]}n, 2a, {Ag[(R)-LMe]}n, 2a', {Cu[(S)-LR]2}n (R = Me, 3a; iPr, 3b), {Cu[(R)-LMe]}n, 3a', {Zn[(S)-LR]2}n (R = Me, 4a; iPr, 4b; (S)-secBu, 4d) and {Zn[(R)-LMe]2}n, 4a'. For the known compounds 3a and 4a, this procedure is a new synthetic route that avoided high temperature reaction conditions. New complexes 2, 3a', b, and 4a', b, d were characterised by elemental analysis, infrared and XRPD methods and complex 2a by single-crystal X-ray diffraction. This complex is also a two-dimensional coordination polymer in which the [(S)-LMe]- anion acts as a µ4κN,κ2O,κ2O' bridging ligand. Compounds 1-4a' are the first examples of homochiral coordination polymers with imidazole-monocarboxylate ligands based on non-natural amino acids. Preliminary studies on the metal-catalysed preparation of chiral α-aminophosphonates were carried out but, unfortunately, no enantioselectivity was observed.

12.
Sensors (Basel) ; 19(4)2019 Feb 19.
Artículo en Inglés | MEDLINE | ID: mdl-30791495

RESUMEN

Dopamine, norepinephrine, and epinephrine neurotransmitters can be detected by electrochemical oxidation in conventional electrodes. However, their similar chemical structure and electrochemical behavior makes a difficult selective analysis. In the present work, glassy carbon electrodes have been modified with silica layers, which were prepared by electroassisted deposition of sol⁻gel precursors. These layers were morphologically and compositionally characterized using different techniques, such as field emission scanning electron microscopy (FESEM), TEM, FTIR, or thermogravimetric analysis⁻mass spectrometry (TG-MS). The affinity of silica for neurotransmitters was evaluated, exclusively, by means of electrochemical methods. It was demonstrated that silica adsorbs dopamine, norepinephrine, and epinephrine, showing different interaction with silica pores. The adsorption process is dominated by a hydrogen bond between silanol groups located at the silica surface and the amine groups of neurotransmitters. Because of the different interaction with neurotransmitters, electrodes modified with silica films could be used in electrochemical sensors for the selective detection of such molecules.


Asunto(s)
Técnicas Biosensibles/métodos , Dopamina/aislamiento & purificación , Epinefrina/aislamiento & purificación , Norepinefrina/aislamiento & purificación , Dopamina/química , Técnicas Electroquímicas , Electrodos , Epinefrina/química , Humanos , Microscopía Electrónica de Rastreo , Neurotransmisores/química , Neurotransmisores/aislamiento & purificación , Norepinefrina/química , Oxidación-Reducción , Gel de Sílice/química
14.
Molecules ; 23(7)2018 06 30.
Artículo en Inglés | MEDLINE | ID: mdl-29966332

RESUMEN

Chiral alkyl aryl sulfoxides were obtained by molybdenum-catalyzed oxidation of alkyl aryl sulfides with hydrogen peroxide as oxidant in mild conditions with high yields and moderate enantioselectivities. The asymmetry is generated by the use of imidazolium-based dicarboxylic compounds, HLR. The in-situ-generated catalyst, a mixture of aqueous [Mo(O)(O2)2(H2O)n] with HLR as chirality inductors, in the presence of [PPh4]Br, was identified as the anionic binuclear complex [PPh4]{[Mo(O)(O2)2(H2O)]2(µ-LR)}, according to spectroscopic data and Density Functional Theory (DFT) calculations. A nonclassical hydrogen bond between one C⁻H bond of the alkyl R group of coordinated (LR)− and one oxygen atom of the peroxido ligand was identified as the interaction responsible for the asymmetry in the process. Additionally, the step that governs the enantioselectivity was theoretically analyzed by locating the transition states of the oxido-transfer to PhMeS of model complexes [Mo(O)(O2)2(H2O)(κ¹-O-LR)]− (R = H, iPr). The ∆∆G≠ is ca. 0 kcal∙mol−1 for R = H, racemic sulfoxide, meanwhile for chiral species the ∆∆G≠ of ca. 2 kcal∙mol−1 favors the formation of (R)-sulfoxide.


Asunto(s)
Molibdeno/química , Catálisis , Enlace de Hidrógeno , Peróxido de Hidrógeno/química , Estructura Molecular , Oxidación-Reducción , Safrol/análogos & derivados , Safrol/química , Estereoisomerismo
15.
Materials (Basel) ; 11(6)2018 Jun 14.
Artículo en Inglés | MEDLINE | ID: mdl-29904009

RESUMEN

A study on the electrochemical oxidation of piperazine and its electrochemical copolymerization with aniline in acidic medium is presented. It was found that the homopolymerization of piperazine cannot be achieved under electrochemical conditions. A combination of electrochemistry, in situ Fourier transform infrared (FTIR), and ex situ X-ray photoelectron spectroscopy (XPS) spectroscopies was used to characterize both the chemical structure and the redox behavior of an electrochemically synthesized piperazine⁻aniline copolymer. The electrochemical sensing properties of the deposited material were also tested against ascorbic acid and dopamine as redox probes.

16.
Dalton Trans ; 47(1): 197-208, 2017 Dec 19.
Artículo en Inglés | MEDLINE | ID: mdl-29199734

RESUMEN

Oxidoperoxido-molybdenum(vi) complexes containing acylpyrazolonate ligands were obtained by reaction of [Mo(O)(O)2(H2O)n] with the corresponding acylpyrazolone compounds HQR. Complexes Ph4P[Mo(O)(O2)2(QR)] (R = neopentyl, 1; perfluoroethyl, 2; hexyl, 3; phenyl, 4; naphthyl, 5; methyl, 6; cyclohexyl, 7; ethylcyclopentyl, 8) were obtained if the reaction was carried out with one equivalent of HQR in the presence of Ph4PCl. Alternatively, neutral complexes [Mo(O)(O2)(QR)2] (R = neopentyl, 9; hexyl, 10; cyclohexyl, 11) were formed when two equivalents of HQR were used in the reaction. These complexes were isolated in good yields as yellow or yellow-orange crystalline solids and were spectroscopically (IR, 1H, 13C{1H} and 31P{1H} NMR), theoretically (DFT) and structurally characterised (X-ray for 1, 2, 9 and 10). Compounds 1 and 9 were selected to investigate their catalytic behaviour in epoxidation of selected alkenes and oxidation of selected sulphides, while 10 and 11 were tested as catalyst precursors in the deoxygenation of selected epoxide substrates to alkenes, using PPh3 as the oxygen-acceptor. Complexes Ph4P[Mo(O)(O2)2(QR)] were shown to be poor catalyst precursors in oxidation reactions, while the activity of [Mo(O)(O2)(QR)2] species is good in all the studied reactions and comparable to related oxidoperoxido-molybdenum(vi) complexes. Complex [Mo(O)2(QC6)2], 12, was obtained by treatment of 10 with one equivalent of PPh3, demonstrating that the first step in the epoxide deoxygenation mechanism was the oxygen atom transfer toward the phosphane.

17.
Dalton Trans ; 46(2): 471-482, 2017 Jan 03.
Artículo en Inglés | MEDLINE | ID: mdl-27966716

RESUMEN

Different novel coordination polymers containing zinc, 1-4, and copper, 5-8, metals, connected via chiral imidazolium-based dicarboxylate ligands, [LR]-, were isolated by reaction between zinc acetate or copper acetate and enantiomerically pure HLR compounds. They were characterised and structurally identified by X-ray diffraction methods (single crystal and powder). These compounds are two-dimensional homochiral coordination polymers, [M(LR)2]n, in which the metal ions are coordinated by the two carboxylate groups of [LR]- anions in a general bridging monodentate µ2-κ1-O1,κ1-O3 fashion that afforded tetrahedral metal coordination environments for zinc, 1-4, and square planar for copper, 5-8, complexes. In all the compounds the 3D supramolecular architecture is constructed by non-covalent interactions between the hydrophobic parts (R groups) of the homochiral 2D coordination polymers and, in some cases, by weak C-HO non-classical hydrogen bonds that provided, in general, a dense crystal packing. DFT calculations on the [LR]- anions confirmed their conformational flexibility as ditopic linkers and this fact makes possible the formation of different coordination polymers for four-coordinated metal centers. Preliminary studies on the Zn-catalyzed synthesis of chiral α-aminophosphonates were carried out and, unfortunately, no enantioselectivity was observed in these reactions.

18.
Oncotarget ; 7(35): 56083-56106, 2016 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-27528230

RESUMEN

A mutation in the HERC2 gene has been linked to a severe neurodevelopmental disorder with similarities to the Angelman syndrome. This gene codifies a protein with ubiquitin ligase activity that regulates the activity of tumor protein p53 and is involved in important cellular processes such as DNA repair, cell cycle, cancer, and iron metabolism. Despite the critical role of HERC2 in these physiological and pathological processes, little is known about its relevance in vivo. Here, we described a mouse with targeted inactivation of the Herc2 gene. Homozygous mice were not viable. Distinct from other ubiquitin ligases that interact with p53, such as MDM2 or MDM4, p53 depletion did not rescue the lethality of homozygous mice. The HERC2 protein levels were reduced by approximately one-half in heterozygous mice. Consequently, HERC2 activities, including ubiquitin ligase and stimulation of p53 activity, were lower in heterozygous mice. A decrease in HERC2 activities was also observed in human skin fibroblasts from individuals with an Angelman-like syndrome that express an unstable mutant protein of HERC2. Behavioural analysis of heterozygous mice identified an impaired motor synchronization with normal neuromuscular function. This effect was not observed in p53 knockout mice, indicating that a mechanism independent of p53 activity is involved. Morphological analysis showed the presence of HERC2 in Purkinje cells and a specific loss of these neurons in the cerebella of heterozygous mice. In these animals, an increase of autophagosomes and lysosomes was observed. Our findings establish a crucial role of HERC2 in embryonic development and motor coordination.


Asunto(s)
Síndrome de Angelman/patología , Desarrollo Embrionario/fisiología , Factores de Intercambio de Guanina Nucleótido/metabolismo , Proteína p53 Supresora de Tumor/metabolismo , Ubiquitina-Proteína Ligasas/metabolismo , Animales , Línea Celular Tumoral , Cerebelo/patología , Cerebelo/ultraestructura , Femenino , Fibroblastos , Factores de Intercambio de Guanina Nucleótido/genética , Heterocigoto , Homocigoto , Humanos , Inmunohistoquímica , Ratones , Ratones Endogámicos C57BL , Ratones Noqueados , Microscopía Electrónica , Embarazo , Células de Purkinje/patología , Células de Purkinje/ultraestructura , Proteína p53 Supresora de Tumor/genética , Ubiquitina-Proteína Ligasas/genética
19.
Dalton Trans ; 44(14): 6516-25, 2015 Apr 14.
Artículo en Inglés | MEDLINE | ID: mdl-25756702

RESUMEN

Ligand precursors HL(R,Ph) (R = Me, Ph) were synthesised by condensation of acetylacetone and the corresponding N,N-substituted hydrazines and were characterised spectroscopically and structurally. Both in the solid state and in solution they behave as (Z)-keto-enehydrazines and this was confirmed by DFT calculations which showed that this form was the most stable of their possible tautomers. The reaction of HL(R,Ph) compounds with copper acetate and nickel acetate in EtOH afforded the corresponding complexes [M(L(R,Ph))2] (M = Cu, Ni; R = Me, Ph). The methyl-substituted derivatives were structurally characterised by X-ray methods. A four-coordinate environment around the metal centre, where the two L(Me,Ph) ligands act as bidentate N,O-chelators and lie in a pseudo-trans conformation, was found for both compounds. The dihedral angle between the two six-membered metallacycles M(L(Me,Ph)) was 0° for nickel, a typical square planar coordination, meanwhile it was 23° for copper, a square planar slightly distorted to pseudotetrahedral coordination. Copper complexes [Cu(L(R,Ph))2] were tested as catalysts, in combination with TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl radical), for the aerobic oxidation of 4-nitrobenzyl alcohol as the model reaction. An almost complete conversion to the corresponding aldehyde was observed after 1 h at 60 °C and 1 bar of dioxygen, in toluene as the solvent. Importantly, air at atmospheric pressure was also observed to be appropriate for the oxidation, although longer reaction times were required. After the optimization of the reaction conditions, the study was extended to other alcohol substrates and good catalytic activity was found for benzylic-type alcohols, while low yield was found for 1-octanol.

20.
Langmuir ; 30(34): 10531-8, 2014 Sep 02.
Artículo en Inglés | MEDLINE | ID: mdl-25111076

RESUMEN

The direct electron transfer between indium-tin oxide electrodes (ITO) and cytochrome c encapsulated in different sol-gel silica networks was studied. Cyt c@silica modified electrodes were synthesized by a two-step encapsulation method mixing a phosphate buffer solution with dissolved cytochrome c and a silica sol prepared by the alcohol-free sol-gel route. These modified electrodes were characterized by cyclic voltammetry, UV-vis spectroscopy, and in situ UV-vis spectroelectrochemistry. The electrochemical response of encapsulated protein is influenced by the terminal groups of the silica pores. Cyt c does not present electrochemical response in conventional silica (hydroxyl terminated) or phenyl terminated silica. Direct electron transfer to encapsulated cytochrome c and ITO electrodes only takes place when the protein is encapsulated in methyl modified silica networks.


Asunto(s)
Citocromos c/química , Dióxido de Silicio/química , Electroquímica , Transporte de Electrón , Geles/química , Espectrofotometría Ultravioleta
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