首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 203 毫秒
1.
We report on the direct electrochemistry and electrocatalytic properties of myoglobin (Mb) immobilized on a carbon ionic liquid electrode covered with a matrix composed of an ionic liquid, gellan gum, and Pd nanoparticles. UV-vis and FT-IR spectroscopy confirm that Mb retains its native structure in the composite film on the electrode. Scanning electron microscopy reveals that the nanoparticles are deposited on the surface of the Pd electrode. Cyclic voltametry gives a pair of well-defined and quasireversible redox peaks with a formal potential (E 0′) of ?332 mV and a peak-to-peak separation of 64 mV at near-neutral pH value. The modified electrode shows good electrocatalytic activity towards the reduction of hydrogen peroxide, with a linear range between 5.0 μM and 0.27 mM and a detection limit of 1.7 μM (S/N = 3). The apparent Michaelis-Menten constant is 88 μM.
Figure
A pair of well-defined redox peaks appeared on the cyclic voltammogram of Mb-GG-EMIMBF4/Pd/CILE (c) in pH 7.0 phosphate buffer saline at a scan rate of 500 mV·s?1  相似文献   

2.
Direct electron transfer of myoglobin (Mb) was achieved by its direct immobilization on carbon ionic liquid electrode (CILE) with a conductive hydrophobic ionic liquid, 1‐butyl pyridinium hexaflourophosphate ([BuPy][PF6]) as binder for the first time. A pair of well‐defined, quasi‐reversible redox peaks was observed for Mb/CILE resulting from Mb redox of heme Fe(III)/Fe(II) redox couple in 0.1 M phosphate buffer solution (pH 7.0) with oxidation potential of ?0.277 V, reduction potential of ?0.388 V, the formal potential E°′ (E°′=(Epa+Epc)/2) at ?0.332 V and the peak‐to‐peak potential separation of 0.111 V at 0.5 V/s. The average surface coverage of the electroactive Mb immobilized on the electrode surface was calculated as 1.06±0.03×10?9 mol cm?2. Mb retained its bioactivity on modified electrode and showed excellent electrocatalytic activity towards the reduction of H2O2. The cathodic peak current of Mb was linear to H2O2 concentration in the range from 6.0 μM to 160 μM with a detection limit of 2.0 μM (S/N=3). The apparent Michaelis–Menten constant (K and the electron transfer rate constant (ks) were estimated to be 140±1 μM and 2.8±0.1 s?1, respectively. The biosensor achieved the direct electrochemistry of Mb on CILE without the help of any supporting film or any electron mediator.  相似文献   

3.
Reactions of bis(acetylacetonato)oxovanadium(IV) with N??-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide (H2HNB) and 2-hydroxy-N??-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide (H2HHB), respectively, product two oxovanadium(V) species with the formulas [VO(OMe)(HNB)]2 (I) and [VO(OMe)(HHB)] (II). The complexes I and II have been characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group P21/n, a = 8.208(2), b = 14.528(3), c = 16.418(3) ?, ?? = 97.887(3)°, V = 1939.3(7) ?3, Z = 2. The crystal of II is triclinic: space group P $P\bar 1$ a = 8.334(2), b = 10.236(2), c = 11.337(2) ?, ?? = 80.91(3)°, ?? = 75.41(3)°, ?? = 75.63(3)°, V = 902.0(3) ?3, Z = 2. Complex I is a methoxide-bridged dimeric oxovanadium(V) complex, and complex II is a mononuclear oxovanadium(V) complex. The V atom in I is in an octahedral coordination, and that in II is in a square pyramidal coordination.  相似文献   

4.
Quantum chemical calculations using DFT (BP86) and ab initio methods (MP2, MP4 and CCSD(T)) have been carried out for the title compounds. The nature of the Pb?CPb interactions has been investigated with an energy decomposition analysis. The energy minimum structures of the halogen substituted Pb2X2 molecules possess a doubly bridged butterfly geometry A like the parent system Pb2H2. The unusual geometry can be explained with the interactions between PbX fragments in the X 2?? ground state which leads to one Pb?CPb electron-sharing ?? bond and two donor?Cacceptor bonds between the Pb?CX bonds as donor and vacant p(??) AOs of Pb. The energy difference between the equilibrium form A and the linear structure XPb??PbX (E) which is a second-order saddle point is much higher when X is a halogen atom than for X?=?H. This is because the a 4???????X 2?? excitation energies of PbX (X?=?F?CI) are higher than for PbH. The structural isomers B, D1, D2, E, F1, F2 and G of Pb2X2 are no minima on the potential energy surface.  相似文献   

5.
In an effort to probe the reaction of antibiotic hydrolysis catalyzed by B3 metallo-??-lactamase (M??L), the thermodynamic parameters of penicillin G hydrolysis catalyzed by M??L L1 from Stenotrophomonas maltophilia were determined by microcalorimetric method. The values of activation free energy ??G ?? ?? are 88.26, 89.44, 90.49, and 91.57?kJ?mol?1 at 293.15, 298.15, 303.15, and 308.15?K, respectively, activation enthalpy ??H ?? ?? is 24.02?kJ?mol?1, activation entropy ??S ?? ?? is ?219.2511?J?mol?1?K?1, apparent activation energy E is 26.5183?kJ?mol?1, and the reaction order is 1.0. The thermodynamic parameters reveal that the penicillin G hydrolysis catalyzed by M??L L1 is an exothermic and spontaneous reaction.  相似文献   

6.
Two new V(IV) complexes, [VO(Naph?Ctrp)(phen)]·CH3OH (1) and [VO(o-Van?Ctrp)(phen)]·CH3OH·H2O (2) (Naph?CTrp?=?Schiff base derived from 2-hydroxy-1-naphthaldehyde and l-tryptophan, o-Van?Ctrp?=?Schiff base derived from o-vanillin and l-tryptophan, phen?=?1,10-phenanthroline), have been synthesized and characterized by physicochemical methods. The V(IV) atoms in both complexes are six-coordinated in a distorted octahedral environment. In the crystals of complex 1, the C?CH···?? and ?ШC?? stacking interactions form a 1D chain structure, whereas for complex 2, hydrogen bonds connect the molecular units into a 2D plane structure. The DNA binding properties and cleavage efficiencies of the complexes have been investigated by spectroscopic methods, viscosity measurements and agarose gel electrophoresis. The results suggest that both complexes can bind to CT-DNA in an intercalative mode and can also cleave pBR322 DNA.  相似文献   

7.
Mononuclear copper(II) complexes of 1,2,4-triazole-based Schiff base macrocyclic hydrazones, III and IV, have been reported. The prepared amorphous complexes have been characterized by spectroscopic methods, electron spray ionization mass spectrometry, and elemental analysis data. Electrochemical studies of the complexes in DMSO show only one quasi-reversible reduction wave at +0.43 V (ΔE = 70 mV) and +0.42 V (ΔE = 310 mV) for III and IV, respectively, which is assigned to the Cu(II) → Cu(I) reduction process. Temperature dependence of magnetic susceptibilities of III and IV has been measured within an interval of 2–290 K. The values of χM at 290 K are 1.72 × 10?3 cm3 mol?1 and 1.71 × 10?3 for III and IV, respectively, which increases continuously upon cooling to 2 K. EPR spectra of III and IV in frozen DMSO and DMF were also reported. The trend g|| > g⊥ > ge suggests the presence of an unpaired electron in the dx2?y2 orbital of the Cu(II) in both complexes. Furthermore, spectral and antimicrobial properties of the prepared complexes were also investigated.  相似文献   

8.
The AIE luminogen tetrakis(2-naphthalenyl)ethene (2-NA 4 E) was synthesized by Barton’s double extrusion diazo-thione coupling method from 2,2′-dinaphthyl thioketone and 2,2′-(diazomethylene)bisnaphthylene in 77 % yield. The structure of 2-NA 4 E was confirmed by its 1H NMR and 13C NMR spectra with full assignments. 2-NA 4 E and its parent tetraphenylethene (Ph 4 E) have been subjected to a comprehensive computational DFT study, in search of their conformational spaces. Seven conformers and two transition states of 2-NA 4 E have been located. Four conformers and one transition state of Ph 4 E have been located. The conformers of 2-NA 4 E and Ph 4 E are not overcrowded, as indicated by the contact distances in the fjord and cove regions. The relative free energies (ΔG 298) of the six most stable conformers of 2-NA 4 E are in the narrow range of 2.3 kJ/mol; they make comparable contributions (12–29 %) to the equilibrium mixture. The energy barriers for the diastereomerization D 2-Z,Z,Z,Z $ \rightleftharpoons $ ? D 2-E,E,E,E via the transition state C 1-Z,E,E,Z and for the enantiomerization C 2-Z,Z,E,E $ \rightleftharpoons $ ? C 2-E,E,Z,Z via the transition state C i -Z,E,Z,E are only 29.8 and 29.0 kJ/mol, respectively, indicating very rapid rates of diastereomerization and enantiomerization at room temperature. The values of naphthalenyl torsion angles and ethenic twist angles in 2-NA 4 E are almost identical to those in the parent Ph 4 E. The previously proposed “bulkiness” of the naphthalenyl substituents and the validity of the restriction of naphthalenyl rotation are challenged. The analysis of the AIE effect in 2-NA 4 E should take into account the intermolecular homochiral and heterochiral interactions between the conformers.  相似文献   

9.
A nanohybrid biomaterial was fabricated by mixing Co3O4 nanorods, gold nanoparticles (Au-NPs) and myoglobin (Mb), and depositing it on the surface of a carbon paste electrode containing the ionic liquid N-hexylpyridinium hexafluorophosphate as the binder. UV–vis and FT-IR revealed the Mb in the composite film to have remained in its native structure. A pair of well-defined redox peaks appears in cyclic voltammograms and indicates direct electron transfer from the Mb to the underlying electrode. The results are attributed to the favorable orientation of Mb in the composite film, to the synergistic effects of Co3O4 nanorods and Au-NPs. The modified electrode shows excellent electrocatalytic ability towards the reduction of substrates such as trichloroacetic acid and nitrite, and displays good stability and reproducibility.
Figure
A nanohybrid biomaterial composed of Co3O4 nanorods, gold nanoparticles and myoglobin was deposited on the surface of an ionic liquid modified carbon paste electrode. Direct electron transfer of Mb was realized and the electrocatalysis of the modified electrode was investigated.  相似文献   

10.
A new complex [Co(phen)3] · (H3btec) · (H2btec)0.5 · DMF · 6H2O (1) (H4btec = 1,2,4,5-Benzenetetracarboxylic acid, phen = 1,10-phenanthroline, DMF = dimethylformamide) was synthesized by the reaction of pyromellitic dianhydride, phen · H2O and CoSO4 · 7H2O. Complex 1 crystallizes in the triclinic system, space group P-1 with a = 11.8123(14) ?, b = 13.0356(16) ?, c = 17.575(2) ?, ?? = 91.461(2)°, ?? = 101.347(2)°, ?? = 99.830(2)°, FW = 1159.94, Z = 2, V = 2609.5(5) ?3. X-ray crystal structural determination indicates that the Co(II) ion is octahedral coordinated by six nitrogen atoms of three phenanthroline ligands. The [Co(phen)3]2+ cation engages its phen ligands in ??-?? interactions with H2btec anion. Extensive hydrogen bonding interactions occur between water molecules, DMF, H3btec and H2btec anions. The highly-crystalline compounds 1, which are insoluble in water as well as common organic solvents, have been characterized in the solid-state by elemental analysis, thermogravimetric analysis and IR spectra. Moreover, the study of the electrochemistry of complex 1 was carried out by using cyclic voltammetry. It revealed that the Co(II) complex exhibits a quasi-reversible one-electron redox process.  相似文献   

11.
A reaction of ammonium tetra(isothiocyanato)diamminechromate(III) (ammonium reineckate) with ?-caprolactam in aqueous solution at different pH values gave the novel complexes (NH4)[Cr(NH3)2(NCS)4] · 7Cpl (I), (NH4)[Cr(NH3)2(NCS)4] · 2.5Cpl · 0.5(H2O) (II), and (HCpl2)[Cr(NH3)2(NCS)4] (III), where Cpl is ?-caprolactam (?-C6H11NO). The crystals of complexes I?CIII are triclinic, space group $P\bar 1$ ; I: a = 12.7058(4) ?, b = 13.2544(4) ?, c = 19.4487(7) ?, ?? = 105.2360(10)°, ?? = 106.6410(10)°, ?? = 91.5290(10)°, V = 3009.37(17) ?3, ??calc = 1.245 g/cm3, Z = 2; II: a = 12.3144(5) ?, b = 12.6518(5) ?, c = 23.3300(8) ?, ?? = 75.4580(10)°, ?? = 80.0760(10)°, ?? = 61.0830(10)°, V = 3074.1(2) ?3, ??calc = 1.358 g/cm3, Z = 4; III: a = 6.4701(4) ?, b = 12.5973(9) ?, c = 16.5556(12) ?, ?? = 108.769(2)°, ?? = 98.543(2)°, ?? = 90.345(2)°, V = 1261.36(15) ?3, ??calc = 1.437 g/cm3, Z = 2. The structure refinement for (HCpl2)3[Cr(NCS)6] (IV) was revised. Like complex III, complex IV contains the cation (HCpl2)+ stabilized by a strong hydrogen bond between the O atoms of the ?-caprolactam molecules; the cation was structurally characterized for the first time.  相似文献   

12.
We present a modified glassy carbon electrode as a sensing platform for glucose. It is based on a composite film prepared from Ni(II) ion, quercetin and graphene. The sensor was characterized by cyclic voltammetry. The electron transfer coefficient, reaction rate constant and catalytic rate constant were determined and found to be 0.53, 5.4?s?1 and 2.93?×?103?M?1 s?1, respectively. The catalytic current depends linearly on the concentration of glucose in the range from 3 to 900???M, with a detection limit of 0.5???M (at an S/R of 3). The sensor exhibits good reproducibility, stability, fast response, and high sensitivity.
Figure
Cyclic voltammograms of Ni(II)-Qu/Gr/GCE in 0.1?M NaOH solution at various scan rates (from inner to outer): 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0?V·s?1. Plot of I p versus ??1/2 and E p versus log??.  相似文献   

13.
Two new 2D metal-organic complexes, namely [Cu(3-dpyb)(1,2,4-HBTC)(H2O)]·H2O (1) and [Cu3(3-dpyb)3(SIP)2(H2O)8]·6H2O (2) [3-dpyb?=?N,N??-bis(3-pyridinecarboxamide)-1,4-butane, 1,2,4-H3BTC?=?1,2,4-benzenetricarboxylic acid, H3SIP?=?5-sulfoisophthalic acid], have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction analyses. Single crystal X-ray analyses reveal that the two Cu(II) complexes show different 2D coordination networks, the 4-connected (44·62) topology for complex 1 and the (4·62)2(42·62·82) topology for complex 2. In the 2D layers of complexes 1 and 2, the 3-dpyb ligands adopt a typical ?? 2-bridging mode (via ligation of two pyridyl nitrogen atoms), while 1,2,4-HBTC and SIP serve as a linear spacer and a ??V??-like linker, respectively, to connect the adjacent Cu(II) centers. The adjacent 2D layers are extended to 3D supramolecular networks via hydrogen-bonding interactions. The fluorescence properties of both complexes and electrochemical properties of complex 2 have also been investigated. The complex 2 bulk-modified carbon paste electrode (2-CPE) displayed a one-electron redox wave in potential range of 600?C200?mV in 1?M H2SO4 aqueous solution, and 2-CPE showed good electrocatalytic activity toward the reduction of nitrite.  相似文献   

14.
The adsorption properties and acid?Cbase contributions to the surface energy of (E)-N-((E)-3-(4-(dimethylamino)phenyl)allylidene)-4-(4-((E)-((E))-3-(4(dimethylamino)phenyl)allylidene)amino)-3-methylnaphthalen-1-yl)-2-ethylnaphthalen-1-amine which is a new D-??-D Type Schiff base ligand (L) were determined by inverse gas chromatography (IGC) at infinite dilution. The retentions of several organic solvents on L were measured in the temperature range from 40 to 100 °C by IGC. The dispersive component of the surface energy, $ \gamma_{S}^{D} $ of studied adsorbent surface was estimated using retention times of different nonpolar organics in the infinite dilution region. Thermodynamic parameters of adsorption (free energy, $ \Updelta G_{A}^{S} , $ enthalpy, $ \Updelta H_{A}^{S} $ and entrophy, $ \Updelta S_{A}^{S} $ ), dispersive components of the surface energies, $ \gamma_{S}^{D} $ and the acid, K A and base, K D constants for the L were calculated. The obtained results proved that IGC is an efficient and successful technique for the characterization of adsorption properties and acid?Cbase quantity of these kinds of materials.  相似文献   

15.
A series of lanthanide complexes with the 3,4,5-trimethoxybenzoic acid(3,4,5-tmoba) and 1,10-phenanthroline(phen),[Ln(3,4,5-tmoba) 3 phen] 2(Ln = Pr(1),Nd(2) and Ho(3)),have been synthesized and characterized by a series of techniques including elemental analysis,IR spectra,X-ray crystallography and TG/DSC-FTIR technology.The three complexes have two kinds of coordination modes,in which the Pr 3+ and Nd 3+ cations are nine-coordinated and the Ho 3+ cation is eight-coordinated.The three-dimensional IR accumulation spectra of gaseous products for complexes 1-3 were analyzed and the gaseous products were identified by the typical IR spectra obtained from the 3D surface graphs.Meanwhile,we obtained the activation energy E of the first steps of complexes 1-3 by the integral isoconversional non-linear(NL-INT) method and discussed the non-isothermal kinetics of complexes 1-3 using the Malek method.Finally,SB(m,n) was defined as the kinetic method of the first-step thermal decomposition.The thermodynamic parameters △G≠,△H≠ and △S≠ of activation at the peak temperature were also calculated.  相似文献   

16.
The ??-complexes [CuCl(C3H5NHC2H4CN)] (I), [(C3H5NH2C2H4CN)Cu2Cl3] (II), [((C3H5)2NHC2H4CN)CuCl2] (III), and [((C3H5)2NHC2H4CN)CuBr2] (IV) are obtained as single crystals by the ac electrochemical synthesis on copper wire electrodes from ethanolic solutions of 3-(allylamino)propanenitrile, 3-(diallylamino)propanenitrile, and CuX2 (X = Cl, Br). Their crystal structures are determined. The crystals of compounds I, III, and IV are monoclinic, space group P21/c, Z = 4. The crystals of compound II are triclinic, space group P $\bar 1$ , Z = 2. The unit cell parameters are a = 11.125(4), b = 8.769(4), c = 8.570(4) ?, ?? = 90.94(4)°, V = 835.9(6) ?3 (I); a = 6.2566(4), b = 7.5975(6), c = 11.1251(8) ?, ?? = 90.896(6)°, ?? = 92.827(5)°, ?? = 94.340(5)°, V = 526.57(7) ?3 (II); a = 11.656(4), b = 6.992(4), c = 14.681(5) ?, ?? = 100.89(4)°, V = 1174.9(9) ?3 (III); a =11.845(4), b = 7.282(4), c=14.855(5) ?, ?? = 100.37(4)°, V = 1260.4(9) ?3 (IV). The coordination mode of the Cu(I) atom in complex I includes two halogen atoms, the C=C bond, and the secondary amine N atom. The coordination environment in isostructural crystals of complexes III and IV is formed by the C=C bond and three halogen atoms as in complex II.  相似文献   

17.
Shuttle-like Fe2O3 nanoparticles (NPs) were prepared by microwave-assisted synthesis and characterized by scanning electron microscopy and X-ray diffraction. The NPs were immobilized on a glassy carbon electrode and then covered with dsDNA. The resulting electrode gives a pair of well-defined redox peaks for Pb(II) at pH 6.0, with anodic and cathodic peak potentials occurring at ?0.50?V and ?0.75?V (vs. Ag/AgCl), respectively. The amperometric response to Pb(II) is linear in the range from 0.12 to 40?nM, and the detection limit is 0.1?nM at a signal-to-noise ratio of 3. The sensor exhibits high selectivity and reproducibility.
Figure
A fast and sensitive Pb(II) electrochemical sensor has been fabricated by dropping Fe2O3 NPs and double-strand DNA onto the pretreated glassy carbon electrode. The sensor had high sensitivety, high sensitivity, ease of construction and utilization for Pb(II) determination.  相似文献   

18.
Two new manganese complexes of [(2-py)CNOH]2Cl2 (1) and [(2-py)CNOH] 2(OAc) 2 (2) were synthesized and their structures were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. Two complexes were used as bulk modifier to fabricate two carbon paste electrodes (Mn-CPE: 1-CPE and 2-CPE). The electrochemical behaviors of two modified electrodes were characterized by cyclic voltammetry. They have similar electrochemical behaviors and good electrocatalytic activities toward the reduction of hydrogen peroxide and nitrite. The results are reproducible with a lower detection limit than earlier reports. There exist a good linear relationship between peak current with the concentration in the range of 0.10?C1.20 ??M and a detection limit of 0.08 ??M for hydrogen peroxide, and in the range of 0.02?C0.10 ??M and a detection limit of 0.01 ??M for nitrite. Also Mn-CPE exhibits remarkable long term stability, simple preparation and inexpensive material, which is important for practical application on electrochemistry sensors.  相似文献   

19.
An amperometric biosensor for hydrogen peroxide (H2O2) has been constructed by immobilizing cytochrome c on an indium/tin oxide (ITO) electrode modified with a macroporous material. Cyclic voltammetry showed that the direct and quasi-reversible electron transfer of cytochrome c proceeds without the need for an electron mediator. A surface-controlled electron transfer process can be observed with an apparent heterogeneous electron-transfer rate constant (ks) of 29.2?s?1. The biosensor displays excellent electrocatalytic responses to the reduction of H2O2 to give amperometric responses that increase steadily with the concentration of H2O2 in the range from 5???M to 2?mM. The detection limit is 0.61???M at pH?7.4. The apparent Michaelis-Menten constant (Km) of the biosensor is 1.06?mM. This investigation not only provided a method for the direct electron transfer of cytochrome c on macroporous materials, but also established a feasible approach for durable and reliable detection of H2O2.
Figure
Biosensor for hydrogen peroxide was developed by immobilizing cytochrome c in the macroporous ordered silica foam (MOSF) through the electrostatic interaction. The achievement of the direct electron transfer between cytochrome c and electrode surface indicated that the MOSF modified electrode displayed good affinity and biocompatibility for cytochrome c.  相似文献   

20.
Ferritin was immobilized on a glassy carbon electrode with electrodeposited cobalt oxide nanoparticles, and its direct electron transfer behavior was studied. It exhibits a pair of redox peaks due to direct electron transfer between ferritin and the nanoparticles. Electrochemical parameters including the formal potential (E0??), the charge transfer coefficient (??), and the apparent heterogeneous electron transfer rate constant (ks) were determined. The sensor displays excellent biocatalytic activity in terms of reduction of hydrogen peroxide, and this was applied to electrochemical sensing of hydrogen peroxide.
Figure
In this work, cobalt oxide nanoparticles were electrodeposited on the surface of an electrode for immobilization of ferritin molecules to prepare hydrogen peroxide biosensor. The immobilized protein molecules still preserve their biological activities and have great capability in catalyzing the reduction of hydrogen peroxide.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号