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1.
Talanta ; 274: 125995, 2024 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-38599115

RESUMEN

Three-dimensional (3D) porous metal oxide nanomaterials with controllable morphology and well-defined pore size have attracted extensive attention in the field of gas sensing. Herein, hierarchically porous ZnO-450 was obtained simply by annealing Zeolitic Imidazolate Frameworks (ZIF-90) microcrystals at an optimal temperature of 450 °C, and the effect of annealing temperature on the formation of porous nanostructure was discussed. Then the as-obtained ZnO-450 was employed as sensing materials to construct a Micro-Electro-Mechanical System (MEMS) gas sensor for detecting NO2. The MEMS sensor based on ZnO-450 displays the excellent gas-sensing performances at a lower working temperature (190 °C), such as high response value (242.18% @ 10 ppm), fast response/recovery time (9/26 s) and ultralow limit of detection (35 ppb). The ZnO-450 sensor shows better sensing performance for NO2 detection than ZnO-based composites materials or commercial ZnO nanoparticles (NPs), which are attributed to its unique hierarchically structures with high porosity and larger surface area. This ZIFs driven strategy can be expected to pave a new pathway for the design of high-performance NO2 sensors.

2.
ACS Appl Mater Interfaces ; 15(39): 46022-46030, 2023 Oct 04.
Artículo en Inglés | MEDLINE | ID: mdl-37729492

RESUMEN

A new strategy is developed herein to improve the solid fluorescence of thiazolothiazole viologen by using the ZnCl42- cluster as a scaffold to hinder π-stacking. Importantly, the Cl···H bonds are formed in the solid state to sustain the framework and can be automatically dissociated when dissolved in H2O, thus having no impact on the strong emission in aqueous solution. As such, the first case of organic-inorganic viologen-zinc halide named 4PV·ZnCl4 was designed and synthesized, and a significant increase in photoluminescence quantum yield (ΦF) is realized from 4PV·2Br (ΦF = 0%) to 4PV·ZnCl4 (ΦF = 27.0%) in solid and from 97% to 98% in H2O. 4PV·ZnCl4 also displays pH stimuli-responsive naked-eye chromic behavior and photoluminescence with different coloring states and intensities. The multifunctional performance of 4PV·ZnCl4 provides a prerequisite for carrying different information, expanding their promising application in multilevel information encryption.

3.
Chem Sci ; 14(25): 7016-7025, 2023 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-37389262

RESUMEN

The dark-colored viologen radical cations are unstable in air and easily fade, thus greatly limiting their applications. If a suitable substituent is introduced into the structure, it will have the dual function of chromism and luminescence, which will broaden its application field. Here, Vio1·2Cl and Vio2·2Br were synthesized by introducing aromatic acetophenone and naphthophenone substituents into the viologen structure. The keto group (-CH2CO-) on the substituents is prone to isomerize into the enol structure (-CH[double bond, length as m-dash]COH-) in organic solvents, especially in DMSO, resulting in a larger conjugated system to stabilize the molecular structure and enhance fluorescence. The time-dependent fluorescence spectrum shows obvious keto-to-enol isomerization-induced fluorescence enhancement. The quantum yield also increased significantly (T = 1 day, ΦVio1 = 25.81%, ΦVio2 = 41.44%; T = 7 days, ΦVio1 = 31.48%, and ΦVio2 = 54.40%) in DMSO. The NMR and ESI-MS data at different times further confirmed that the fluorescence enhancement was caused by isomerization, and no other fluorescent impurities were produced in solution. DFT calculations show that the enol form is almost coplanar throughout the molecular structure, which is conducive to stabilizing the structure and enhancing fluorescence. The fluorescence emission peaks of the keto and enol structures of Vio12+ and Vio22+ were at 416-417 nm and 563-582 nm, respectively. The fluorescence relative oscillator strength of Vio12+ and Vio22+ enol structures is significantly higher than that of keto structures (f value changes from 1.53 to 2.63 for Vio12+ and from 1.62 to 2.81 for Vio22+), indicating stronger fluorescence emission of the enol structure. The calculated results are in good agreement with the experimental results. Vio1·2Cl and Vio2·2Br are the first examples of isomerization-induced fluorescence enhancement of viologen derivatives, which shows strong solvatofluorochromism under UV light, making up for the disadvantage that it is easy for a viologen radical to fade in air, and providing a new strategy for designing and synthesizing viologen materials with strong fluorescence.

4.
Nanomaterials (Basel) ; 13(11)2023 May 26.
Artículo en Inglés | MEDLINE | ID: mdl-37299647

RESUMEN

In this work, a facile synthesis method was adopted to synthesize MOF-14 with mesoporous structure. The physical properties of the samples were characterized by PXRD, FESEM, TEM and FT-IR spectrometry. By coating the mesoporous-structure MOF-14 on the surface of a quartz crystal microbalance (QCM), the fabricated gravimetric sensor exhibits high sensitivity to p-toluene vapor even at trace levels. Additionally, the limit of detection (LOD) of the sensor obtained experimentally is lower than 100 ppb, and the theoretical detection limit is 57 ppb. Furthermore, good gas selectivity and fast response (15 s) and recovery (20 s) abilities are also illustrated along with high sensitivity. These sensing data indicate the excellent performance of the fabricated mesoporous-structure MOF-14-based p-xylene QCM sensor. On the basis of temperature-varying experiments, an adsorption enthalpy of -59.88 kJ/mol was obtained, implying the existence of moderate and reversible chemisorption between MOF-14 and p-xylene molecules. This is the crucial factor that endows MOF-14 with exceptional p-xylene-sensing abilities. This work has proved that MOF materials such as MOF-14 are promising in gravimetric-type gas-sensing applications and worthy of future study.

5.
Nanomaterials (Basel) ; 12(22)2022 Nov 17.
Artículo en Inglés | MEDLINE | ID: mdl-36432320

RESUMEN

The capture and separation of CO2 is an important means to solve the problem of global warming. MOFs (metal-organic frameworks) are considered ideal candidates for capturing CO2, where the adsorption enthalpy is a crucial indicator for the screening of materials. For this purpose, we propose a new minimalist solution using QCM (quartz crystal microbalance) to extract the CO2 adsorption enthalpy on MOFs. Three kinds of MOFs with different properties, sizes and morphologies were employed to study the adsorption enthalpy of CO2 using a QCM platform and a commercial gas sorption analyzer. A Gaussian simulation calculation and previously data reported were used for comparison. It was found that the measuring errors were between 5.4% and 6.8%, proving the reliability and versatility of our new method. This low-cost, easy-to-use, and high-accuracy method will provide a rapid screening solution for CO2 adsorption materials, and it has potential in the evaluation of the adsorption of other gases.

6.
Nanomaterials (Basel) ; 12(22)2022 Nov 17.
Artículo en Inglés | MEDLINE | ID: mdl-36432321

RESUMEN

Aggregation-induced quenching (ACQ) is a hard problem in fluorescence material, leading to a poor utilization rate of fluorophores. In this work, 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) was synthesized and used as a precursor to build two kinds of fluorescence polymer. The TFFPy molecule with D2h symmetry can easily form polymers with C3 symmetry amines through the Schiff base reaction, making the resulting polymer a 3D amorphous material. Thus, ACQ of fluorophore can be reduced to minimum, making the most usage of the fluorescence of pyrene core. Fluorescence titration and DFT calculation can clearly prove this conclusion. The resulting CPs showed a highly sensitivity to picric acid, down to 3.43 ppm in solution, implying its potential in explosive detection.

7.
Nat Commun ; 13(1): 2850, 2022 May 23.
Artículo en Inglés | MEDLINE | ID: mdl-35606365

RESUMEN

We presented an effective and universal strategy for the improvement of luminophore's solid-state emission, i.e., macrocyclization-induced emission enhancement (MIEE), by linking luminophores through C(sp3) bridges to give a macrocycle. Benzothiadiazole-based macrocycle (BT-LC) has been synthesized by a one-step condensation of the monomer 4,7-bis(2,4-dimethoxyphenyl)-2,1,3-benzothiadiazole (BT-M) with paraformaldehyde, catalyzed by Lewis acid. In comparison with the monomer, macrocycle BT-LC produces much more intense fluorescence in the solid state (ΦPL = 99%) and exhibits better device performance in the application of OLEDs. Single-crystal analysis and theoretical simulations reveal that the monomer can return to the ground state through a minimum energy crossing point (MECPS1/S0), resulting in the decrease of fluorescence efficiency. For the macrocycle, its inherent structural rigidity prohibits this non-radiative relaxation process and promotes the radiative relaxation, therefore emitting intense fluorescence. More significantly, MIEE strategy has good universality that several macrocycles with different luminophores also display emission improvement.

8.
Psychol Health Med ; 27(5): 999-1010, 2022 06.
Artículo en Inglés | MEDLINE | ID: mdl-33048583

RESUMEN

Nurses face a greater risk of needle stick and sharp injuries (NSIs) because they do most of the injections and procedures with sharp instruments. The current study tested a program to improve nurses' knowledge, attitudes and practices on NSIs, three phases were included: Developing the Hospital Practice Standard, implementing a series of measures and implementing of quality supervision phases. It consisted of a bundle of interventions based on Knowledge-Attitudes-Belief-Practice (KAP-KABP) Model with a pretest-posttest design. We obtained a total of 656 (88.53%) completed pre-intervention questionnaires and 674 (92.97%) post-intervention ones. The number of trained participants on NSIs increased from 615 (93.7%) to 666 (98.8%), and reported of NSIs within 3 months decreased from 42 to 15 (2.2%) after the intervention. The total score of Knowledge of NSIs improved from 19.18 (SD = 1.31) to 19.42 (SD = 0.93) after training (Z = -4.025, P < 0.001), the Attitude was raised from 54.21 (SD = 4.09) to 55.24 (SD = 3.59) (Z = -5.261, P < 0.001), and the Practice increased from 89.28 (SD = 7.22) to 92.74 (SD = 7.22), with a P Value<0.05. The findings indicated the program can improve the nurses' knowledge and attitudes towards NSIs prevention. There is a statistically significant increase in the practice score and decrease in the incidence rate of NSIs after the intervention.


Asunto(s)
Lesiones por Pinchazo de Aguja , Competencia Clínica , Conocimientos, Actitudes y Práctica en Salud , Hospitales , Humanos , Lesiones por Pinchazo de Aguja/epidemiología , Lesiones por Pinchazo de Aguja/etiología , Lesiones por Pinchazo de Aguja/prevención & control , Encuestas y Cuestionarios
9.
Inorg Chem ; 60(21): 16370-16377, 2021 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-34677953

RESUMEN

Three new metal-organic frameworks (MOFs), {(CH3NH3)3[Ba2(TTHA)(NO3)(H2O)2]}·2H2O (1), {(CH3NH3)4[Ba3(HTTHA)2(H2O)7]}·3H2O (2), and [Ba7(TTHA)2(NO3)2(H2O)10]·2H2O (3) (H6TTHA = 1,3,5-triazine-2,4,6-triamineh-exaacetic acid) have been synthesized and characterized. The sensing properties of 1-3 were explored with regard to volatile organic compounds (VOCs) by the quartz crystal microbalance (QCM) technique. The results indicated that 1 and 2 have a much higher selectivity and response to chloromethanes (CH2Cl2, CHCl3, and CCl4) compared with H2O, CH3OH, CH3CH2OH, CH3CN, (CH3)2CO, C6H6, C6H5CH3, C6H5CH2CH3, and C6H5Cl at room temperature. Furthermore, 1 and 2 sensing film also exhibits excellent reversibility and stability, and the response and recovery times are almost within 10 s. 3 displays a lower response and poor selectivity to the above VOCs. The significant difference may be caused by their different structural characteristics. The Ba2+ ions are all decacoordinated in 1 and 2, while Ba2+ ions have more open metal sites in 3. So, the high selectivity and response of 1 and 2 may be due to the exchange of coordination water molecules with chloromethanes and possible electrostatic effects between (CH3NH3)+ cations and chloromethanes containing more electronegative Cl atoms. DFT calculation results show that the bond energy of Ba-Cl and Ba-O is not much different, so chloromethanes at high concentrations may exchange coordination water to form weak Ba···Cl interactions and show higher response values. 3 has no obvious VOCs selectivity and higher response due to more open sites of Ba2+ ions and smaller pore size. This work develops a fast and effective method to detect chloromethanes, providing a new opportunity for designing QCM gas sensors coated with different MOF materials.

10.
Dalton Trans ; 48(15): 5035-5047, 2019 Apr 09.
Artículo en Inglés | MEDLINE | ID: mdl-30916697

RESUMEN

A complexone analog chemosensor, H2L, bearing chelating bis(2-pyridylmethyl) amine and alizarin groups was synthesized via the Mannich reaction. H2L chromically responds to OH-, F-, CH3COO-, and H2PO4- in DMF, CH3CN, and acetone, but not in CH3OH or H2O. The addition of F- ions to H2L selectively induces a significant and visible color change in acetonitrile and shifts both methylene proton signals upfield. H2L also exhibits visible responses to Mg2+, Sr2+, Ba2+, Tb3+, Cu2+, Co2+, Ni2+, Zn2+, Mn2+, Cd2+, and Fe3+ in solution. AlCl3 can form an Al : L = 2 : 3 complex that not only changes the color of the DMF solution, but also significantly increases its fluorescence intensity. The limit of fluorescence turn-on detection for AlCl3 in DMF is 2.7 × 10-8 M, which is an order higher than those of other anthraquinone sensors reported in the literature. NMR spectroscopy shows that hydroxyl is not deprotonated upon interacting with Al3+, but will be partially deprotonated in the presence of Zn2+. Contrary to the complexone, the H2L-Ce(iii) complex does not react chromically to F-. However, the H2L-NiCl2 complex responds chromically to F-, with higher sensitivity (LOD = 1.3 × 10-6 M F- in acetonitrile) than free H2L. The spectral changes in the presence of F- are similar to that of OH-; however, the spectrum shifts slightly to a longer wavelength and is more sensitive to both H2L and the H2L-NiCl2 complex. Moreover, 4% or less H2O in the solvent essentially has no influence on the F- sensitivity; however, high water content significantly decreases the F- sensitivity. The spectral changes of the Zn2+, Cu2+, Fe3+, Ce3+, and Ni2+ complexes in the presence of different NaOH concentrations were also investigated.

11.
Chem Commun (Camb) ; 54(47): 5972-5975, 2018 Jun 08.
Artículo en Inglés | MEDLINE | ID: mdl-29789816

RESUMEN

An anionic sod-type zeolitic metal-organic framework [(CH3)2NH2]9{Tb6(η6-TATAT)4(H2O)12}·3Cl·DMA·7H2O [1, H6TATAT = 5,5',5''-(1,3,5-triazine-2,4,6-triyltriimino)tri-1,3-benzenedicarboxylic acid] has been synthesized by metal-ligand directed assembly of hexacarboxylic acid units and Tb3+ ions. Compound 1 with extra-large cavities can efficiently extract natural product anthocyanins from blackberries and release them rapidly into NaCl aqueous solution. And, the nature of the anionic framework makes it very sensitive to detect cationic methyl viologen (MV2+) with a detection limit as low as 1 × 10-8 M.

12.
Chemistry ; 23(33): 8025-8031, 2017 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-28421635

RESUMEN

A homochiral mixed-valence cobalt cluster [CoΙΙ16 CoΙΙΙ4 (µ6 -O)4 (µ3 -OH)12 (S-bme)12 (OAc)6 ]Cl6 ⋅5 CH3 OH⋅18 H2 O (1, Hbme=1H-(benzimidazol-2-yl)ethanol) was synthesized from a racemic ligand and three cobalt salts of CoCl2 ⋅6 H2 O, Co(Ac)2 ⋅4 H2 O and Co(NO3 )2 ⋅6 H2 O in a DMF/MeOH mixed solvent. The enantioselective coordination occurs when a large excess of cobalt ions added in the solution and only the S-configuration of the racemic ligand involved in crystallization. The CD spectra of three crystal samples show identical Cotton signals, indicating the repeatability and the enantiomeric purity of the single crystals. This compound presents a beautiful two-shell Matryoshka-type supertetrahedral T4 cluster constructed by an inner CoΙΙΙ4 O4 cubane and four exterior CoΙΙ4 O4 cubanes bridged by µ6 -O2- and µ3 -OH- ions. This highest nuclear chiral cobalt cluster is the first example of enantiopure cobalt cluster separated from a racemic ligand and is the largest supertetrahedral cobalt cluster up to now. The magnetic studies reveal it behaves as a ferromagnet. Photocatalytic properties of 1 show high catalytic activities for the degradation of the highly toxic triphenyl dye crystal violet (CV) in the presence of H2 O2 under visible light in aqueous solution. The degradation rate almost reach 100 % at 45 min and can maintain 98.54 % after 8 cycles.

13.
ACS Omega ; 2(3): 1128-1133, 2017 Mar 31.
Artículo en Inglés | MEDLINE | ID: mdl-31457495

RESUMEN

Electron-withdrawing/coordinating o-phenolacetyl-substituted viologen can act as a visual sensor for solvents, bases, and temperature in organic solvents. Due to chelating phenolacetyl groups, this viologen can coordinate to Fe(III), Cu(II), and ZnCl2 in aqueous and DMF solutions. Interestingly, this viologen can respond to temperature, grind, and NH3 vapor in its solid state. Stimuli response is visible, fast, and fully reversible in air at room temperature. The color change is attributed to the enolic and/or free radical structure. This is the most versatile chromic material that responds to chemical and physical stimuli in both solution and solid state.

14.
ACS Appl Mater Interfaces ; 7(26): 14493-500, 2015 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-26066088

RESUMEN

Viologen cations are excellent electro- and photochromic materials. They generally have no response or very low sensitivity to bases. In this paper, three compounds, 1,1'-bis(2-oxo-2-phenylethyl)-4,4'-bipyridinium (viologen) with different substituents, including H (1), Cl (2), and OH (3), were synthesized. All three, especially 1 and 2, have very high sensitivity to base in both solution and solid state in air atmosphere. These viologens are responsive not only to bases but also to solvent polarity. NMR shows 1 became enolic and then a radical, whereas 3 is colored only in the radical form. These results are in agreement with EPR spectra. Crystal structures show that the C-C that links two pyridinium and N-C distances in coplanar pyridinium in the colored (radical) form is clearly longer than that of the pale-yellow form, indicating that the color is due to the viologen radical. Viologens containing an electron-withdrawing phenacetyl group are the most sensitive compounds for fast, naked eye detection of base and solvent polarity.

15.
Dalton Trans ; 44(17): 7770-3, 2015 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-25857286

RESUMEN

A new porous metal-organic framework (MOF) {[Cu4(OH)2(tci)2(bpy)2]·11H2O} (1) based on a tetranuclear copper cluster with intracluster antiferromagnetic interactions was synthesized. Quartz crystal microbalance (QCM) sensor studies reveal sensitive and selective sensing for small molecules.

16.
Chem Commun (Camb) ; 50(93): 14674-7, 2014 Dec 04.
Artículo en Inglés | MEDLINE | ID: mdl-25317497

RESUMEN

Two rht anionic metal-organic frameworks were synthesized. There are six [M(H2O)6](2+) ions held together by a super-strong H-bond and arranged in a regular octahedron in each medium cage. Dye adsorption studies revealed a rapid and selective adsorption of cationic dyes and the adsorbed dyes can be released in saturated NaCl aqueous solution.


Asunto(s)
Colorantes/química , Nanoestructuras/química , Compuestos Organometálicos/química , Adsorción , Aniones/química , Cationes/química , Modelos Moleculares , Compuestos Organometálicos/síntesis química , Propiedades de Superficie , Agua/química
17.
Dalton Trans ; 43(21): 7964-78, 2014 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-24715002

RESUMEN

A new neuromelanin-like ketocatechol-containing iminodiacetic acid ligand, (N-(3,4-dihydroxyl)phenacylimino)diacetic acid (H4L), which is also quite similar to compounds found in insect cuticle, has been synthesized and characterized. The X-ray crystal structure of H4L has been successfully determined. Proton binding and coordination with Fe(III), Cu(II), and Zn(II) have been studied by potentiometric titrations and UV-vis spectrophotometry in aqueous solution. UV spectra of H4L in the absence and presence of different metal ions indicate complexes formed with the catechol moiety of H4L in aqueous solution. Visible spectra and NMR reveal that H4L with Fe(III), Cu(II), and Zn(II) can all give stable mono-(ML) and dinuclear complexes [M(ML)]. Fe(III) can also form {Fe(FeL)2} and {Fe(FeL)3} species with sufficient base. The process is accompanied by a drastic color change from light blue to deep-blue to wine-red. The Fe(III)-Cu(II) heteronuclear complex also exists in aqueous solution whose spectra are similar to the homonuclear Fe(III) complex. However, the spectra of {Fe(CuL)} shifted to a longer wavelength and {Fe(CuL)2} and {Fe(CuL)3} shifted to a shorter wavelength. Keto-enol tautomerism was observed in weak basic aqueous solution as indicated by (1)H NMR spectra. The reaction products of Cu(II) complex with H2O2 depend on the H2O2 concentration and pH value. Low concentrations of H2O2 oxidize H4L to a series of semiquinone and quinone compounds with absorption maxima at 314-400 nm, while a high concentration of H2O2 oxidizes H4L to colorless muconic acid derivatives. NaIO4 gives different oxidase products, but no 2,4,5-trihydroxyphenylalanine quinone (TPQ)-like hydroxyquinone can be found.


Asunto(s)
Catecoles/química , Complejos de Coordinación/química , Cobre/química , Compuestos Férricos/química , Peróxido de Hidrógeno/química , Iminoácidos/química , Zinc/química , Catecoles/síntesis química , Complejos de Coordinación/síntesis química , Cristalografía por Rayos X , Compuestos Férricos/síntesis química , Iminoácidos/síntesis química , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Oxidación-Reducción , Espectrofotometría Ultravioleta , Agua/química
18.
Artículo en Inglés | MEDLINE | ID: mdl-23856042

RESUMEN

Aspartic functionalized water-soluble perylene diimide, N,N'-di(2-succinic acid)-perylene-3,4,9,10-tetracarboxylic diimide (PASP) has two absorbance maximums at 527 and 498nm (ε≈1.7×10(4)Lcm(-1)mol(-1)) and two emission peaks at 547 and 587nm respectively. Emission intensities decrease with the increase of PASP concentrations in 20-100µM ranges. Spectral titrations demonstrate that each PASP can coordinate to two Cu(2+) ions in the absence of HEPES buffer. Its stability constant is estimated to be about 1.0×10(12)L(2)mol(-2) at pH 7.20 and its coordinate stoichiometry increased to 7.5 in the same pH in the presence of HEPES buffer. The emission of PASP will be completely quenched upon formation of Cu(2+) complex. The lowest "turn-off" fluorescence detection limit was calculated to be 0.3µM Cu(2+). PASP-Cu solution was used as a "turn-on" fluorescence biosensor to detect ATP. The sensitivity towards ATP is 0.3µM in 50mM HEPES buffer at pH 7.20, which is one of the most sensitive fluorescence sensors.


Asunto(s)
Adenosina Trifosfato/análisis , Ácido Aspártico/química , Técnicas Biosensibles , Cobre/análisis , Colorantes Fluorescentes/química , Imidas/química , Perileno/análogos & derivados , Absorción , Ácido Aspártico/metabolismo , Concentración de Iones de Hidrógeno , Imidas/metabolismo , Perileno/química , Perileno/metabolismo , Solubilidad , Espectrometría de Fluorescencia , Espectrofotometría Ultravioleta , Agua
19.
Dalton Trans ; 42(30): 10898-911, 2013 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-23787993

RESUMEN

Two new m-xylene/cyclohexane-linked bis-aspartic acid ligands, L(b) and L(c), were synthesized via Michael addition in basic aqueous solution. Their structures were characterized by elemental analysis, NMR and MS spectrometry. Both ligands react with Cu(II) and Zn(II) to form dinuclear complexes, with M2L(OH)(-) the major species in neutral/weak basic aqueous solution. To quantify the relative interaction strength between a Lewis acid and base, a new parameter σ = log K/14 was proposed which compares the stability constant with the binding constant between H(+) and OH(-). The dinuclear copper complexes (L(b)-2Cu and L(c)-2Cu) react with H2O2 in aqueous solution. The reaction in 0.020 M phosphate buffer at pH 7.5 is first-order for [L(c)-2Cu], but second-order for [L(b)-2Cu]. The oxidation products are oxygenated and/or dehydrogenated species. Radical trapping tests indicate that both complexes slightly scavenge the OH˙ radical, but generate the H˙ radical. L(c)-2Cu generates the H˙ radical much more effectively than that of L(b)-2Cu when reacted with H2O2. Both complexes are excellent catalysts for the oxidation of nitrobenzene in the presence of H2O2 in weakly basic aqueous solution. The oxidation follows the rate-law v = k[complex][nitrobenzene][H2O2]. The k values in pH 8.0 phosphate buffer at 25 °C are 211.2 ± 0.3 and 607.9 ± 1.7 mol(-2) L(2) s(-1) for L(b)-2Cu and L(c)-2Cu, respectively. The Arrhenius activation energies are 69.4 ± 2.2 and 70.0 ± 4.3 kJ mol(-1) for L(b)-2Cu and L(c)-2Cu, respectively, while the Arrhenius pre-exponential factors are 2.62 × 10(14) and 1.06 × 10(15), respectively. The larger pre-exponential factor makes L(c)-2Cu more catalytically active than L(b)-2Cu. These complexes are some of the most effective oxidation catalysts known for the oxidation of nitrobenzene.


Asunto(s)
Ácido Aspártico/química , Complejos de Coordinación/química , Cobre/química , Hexanos/química , Nitrobencenos/química , Oxígeno/química , Xilenos/química , Zinc/química , Catálisis , Complejos de Coordinación/síntesis química , Ciclización , Oxidación-Reducción , Soluciones , Agua/química
20.
Dalton Trans ; 42(4): 1033-8, 2013 Jan 28.
Artículo en Inglés | MEDLINE | ID: mdl-23108481

RESUMEN

Two chain compounds built with anti-anti acetate bridged Mn(III)(3)O units, [Mn(3)O(Clppz)(3)(EtOH)(4)(OAc)](n) (1) and [Mn(3)O(Clppz)(3)(EtOH)(2)(OAc)](n) (2), were synthesized and characterized. The magnetic studies indicate that 1 is a single-chain magnet with two slow magnetization relaxation processes which has for the first time been found in this type of chain complex, while 2 shows a field-induced metamagnetic behavior. The quite different magnetic behaviors resulted from the different number of coordinated ethanol molecules on the Mn(III)(3)O unit, four ethanol molecules for 1, and two ethanol molecules for 2. The best fittings to the experimental magnetic susceptibilities gave J(1) = -2.72 cm(-1), J(2) = -4.34 cm(-1), zJ = 1.24 cm(-1) for 1 and J(1) = -5.91 cm(-1), J(2) = -0.98 cm(-1), zJ = 1.71 for 2 above 30 K. The positive zJ values indicate the presence of weak ferromagnetic interactions between the trinuclear units via acetate bridges in 1 and 2.

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