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241.
Self‐Assembly Mechanism of Nanoparticles of Ni‐Based Prussian Blue Analogues at the Air/Liquid Interface: A Synchrotron X‐ray Reflectivity Study
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Dr. Juan J. Giner‐Casares Dr. Miguel Clemente‐León Prof. Dr. Eugenio Coronado Prof. Dr. Gerald Brezesinski 《Chemphyschem》2015,16(12):2549-2555
Prussian Blue analogue (PBA) nanoparticles can be self‐assembled at air/liquid interfaces to build novel materials with interesting magnetic features. Herein, we study the influence of the size of PBA Cs0.4Ni[Cr(CN)6]0.9 and K0.25Ni[Fe(CN)6]0.75 nanoparticles on the self‐assembly behavior by synchrotron X‐ray reflectivity. Both nanoparticles show similar Z‐potential values. The phospholipid dipalmitoylphosphatidylcholine and the amino surfactant dimethyldioctadecylammonium have been used as Langmuir monolayers to anchor the PBA nanoparticles and study the interplay of forces directing the self‐assembly of the nanoparticles at the surfactant/liquid interface. Whereas Cs0.4Ni[Cr(CN)6]0.9 nanoparticles with a diameter of 8 nm form an incomplete layer at the surfactant/water interface, the larger K0.25Ni[Fe(CN)6]0.75 nanoparticles with a diameter of 20 nm generate complete layers that can be stacked to one another. The size of the PBA nanoparticles is the main parameter determining the final arrangement at the air/liquid interface, due to the different extent of interparticle interaction. This study aims at the rationale design of PBA nanoparticles for an effective interfacial self‐assembly, ultimately leading to functional materials. 相似文献
242.
Donato Cecere Eugenio Giacomazzi Franca R. Picchia Nunzio Arcidiacono Filippo Donato Roberto Verzicco 《Flow, Turbulence and Combustion》2011,86(3-4):667-688
A progress variable/flame surface density/probability density function method has been employed for a Large Eddy Simulation of a CH4/Air turbulent premixed bluff body flame. In particular, both mean and variance of the progress variable are transported and subgrid spatially filtered gradient contributes to model the flame surface density (that introduces the effect of the subgrid flame reaction zone) and to presume a probability density function (that introduces the effect of subgrid fluctuations on chemistry). Chemistry is preliminarly tabulated in terms of laminar premixed flames and enthalpy is included as a new coordinate in their tabulation to take into account heat losses in the flowfield. Then, the PDF is used to build a turbulent flamelet library. The filtered mass, momentum, enthalpy and scalar equations mentioned above are integrated by an explicit scheme using finite differences, 2nd?Corder accurate in space and third order in time, over a cylindrical non-uniform grid using a staggered mesh. The bluff-body geometry is modelled by using the Immersed Boundary Method. The numerical predictions are compared with the available experimental data. 相似文献
243.
Escobar FM Sabini MC Zanon SM Cariddi LN Tonn CE Sabini LI 《Natural product communications》2011,6(7):989-991
Verbascum thapsus L. is a medicinal plant and has been used to treat numerous pulmonary diseases, asthma, inflammatory disease, spasmodic coughs and migraine headaches. Several studies have demonstrated that different extracts of V. thapsus present antimicrobial activity. Thus, the goal of this study was to evaluate the genotoxic and cytotoxic activities of a methanolic extract of Verbascum thapsus, using micronucleus test in mouse bone marrow. No toxicity in bone marrow was detected in the extract-treated groups. The methanolic extract of V. thapsus at doses of 100, 300 and 500 mg/kg, did not produce a significant increase in the frequency of MNPCE in bone marrow and neither altered the relationship PCE/NCE respect to negative control. These cytogenotoxic findings contribute the preclinical knowledge of methanolic extract of V. thapsus and provide security in its use as herbal medicine. 相似文献
244.
The syntheses, structures, and magnetic properties of compounds of formula [Fe(III)(5-Clsal(2)-trien)][Mn(II)Cr(III)(ox)(3)]·0.5(CH(3)NO(2)) (1), [Fe(III)(5-Brsal(2)-trien)][Mn(II)Cr(III)(ox)(3)] (2), and [In(III)(5-Clsal(2)-trien)][Mn(II)Cr(III)(ox)(3)] (3) are reported. The structure of the three compounds, which crystallize in the orthorhombic P2(1)2(1)2(1) chiral space group, presents a 3D chiral anionic network formed by Mn(II) and Cr(III) ions linked through oxalate ligands with inserted [Fe(III)(5-Clsal(2)-trien)](+), [Fe(III)(5-Brsal(2)-trien)](+), and [In(III)(5-Clsal(2)-trien)](+) cations. The magnetic properties indicate that the three compounds undergo long-range ferromagnetic ordering at ca. 5 K. On the other hand, the inserted Fe(III) cations undergo a partial spin crossover in the case of 1 and 2. 相似文献
245.
Complexation of VO(2+) ion with the most abundant class of human immunoglobulins, immunoglobulin G (IgG), was studied using EPR spectroscopy. Differently from the data in the literature which report no interaction of IgG with vanadium, in the binary system VO(2+)/IgG at least three sites with comparable strength were revealed. These sites, named 1, 2, and 3, seem to be not specific, and the most probable candidates for metal ion coordination are histidine-N, aspartate-O or glutamate-O, and serinate-O or threoninate-O. The mean value for the association constant of (VO)(x)IgG, with x = 3-4, is log β = 10.3 ± 1.0. Examination of the ternary systems formed by VO(2+) with IgG and human serum transferrin (hTf) and human serum albumin (HSA) allows one to find that the order of complexing strength is hTf ? HSA ≈ IgG. The behavior of the ternary systems with IgG and one insulin-enhancing agent, like [VO(6-mepic)(2)], cis-[VO(pic)(2)(H(2)O)], [VO(acac)(2)], and [VO(dhp)(2)], where 6-mepic, pic, acac, and dhp indicate the deprotonated forms of 6-methylpicolinic and picolinic acids, acetylacetone, and 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone, is very similar to the corresponding systems with albumin. In particular, at the physiological pH value, VO(6-mepic)(IgG)(OH), cis-VO(pic)(2)(IgG), and cis-VO(dhp)(2)(IgG) are formed. In such species, IgG coordinates nonspecifically VO(2+) through an imidazole-N belonging to a histidine residue exposed on the protein surface. For cis-VO(dhp)(2)(IgG), log β is 25.6 ± 0.6, comparable with that of the analogous species cis-VO(dhp)(2)(HSA) and cis-VO(dhp)(2)(hTf). Finally, with these new values of log β, the predicted percent distribution of an insulin-enhancing VO(2+) agent between the high molecular mass (hTf, HSA, and IgG) and low molecular mass (lactate) components of the blood serum at physiological conditions is calculated. 相似文献
246.
Moliner-Martínez Y Ribera A Coronado E Campíns-Falcó P 《Journal of chromatography. A》2011,1218(16):2276-2283
A magnetic material based on Fe(3)O(4) magnetic nanoparticles incorporated in a silica matrix by using a sol-gel procedure has been used to extract and preconcentrate emerging contaminants such as acetylsalicylic acid, acetaminophen, diclofenac and ibuprofen from environmental water samples prior to the analysis with Capillary LC-MS. The use of the proposed silica supported Fe(3)O(4) magnetic nanoparticles enables surfactant free extracts for the analysis with MS detection without interferences in the ionisation step. Under the optimum conditions, we demonstrated the reusability of the magnetic sorbent material during 20 uses without loss in the extraction efficiency. In addition, no cleanup was necessary. The preconcentration factor was 100 and the detection limits were between 50 and 150 ng/L. The proposed procedure has been applied to the analysis of water samples obtaining recoveries between 80 and 110% and RSD values lower than 12%. Concentrations of the target analytes over the range 1.7 and 0.1 μg/L have been found in different water samples. 相似文献
247.
Lapolla A Molin L Seraglia R Sechi A Cosma C Bonfante L Chilelli NC Ragazzi E Traldi P 《European journal of mass spectrometry (Chichester, England)》2011,17(3):245-253
The development of new analytical methodologies related to the proteome for the evaluation of renal physiology and pathology is surely of wide interest for physicians, giving them new tools for monitoring complications associated with diabetes, such as end-stage renal disease. In the present study, the clinical significance of the urinary abundance of two peptides, SGSVIDQSRVLNLGPITR (the uromodulin precursor, m/z 1912) and IGPHypGPHypGLMGPP [present in the collagen-α-5(IV) chain precursor, m/z 1219], detected by matrix- assisted laser desorption/ionisation mass spectrometry (MALDI/MS) in microalbuminuric or nephropathic diabetic patients and in non-diabetic nephropathic patients was evaluated. A progressive increase in the abundance of the ion at m/z 1219 and a decrease in the abundance of the ion at m/z 1912 have been found in diabetic microalbuminuric, diabetic-nephropathic and nephropathic patients. Linear correlations are present between serum creatinine values and the abundances of the ions at m/z 1219 (positive correlation, r=0.3645, P<0.0001) and at m/z 1912 (negative correlation, r=-0.3053, P<0.0005). Correlations between the MALDI data and the estimated glomerular filtration rate were also found, while relationships with urinary albumin excretion were found only in sub-sets of patients. Analysis of receiver operating characteristic curves showed a sensitivity up to 96% and a specificity of up to 84% for the two ionic species, or their ratio, for distinguishing diabetic patients with different degrees of nephropathy from healthy subjects, proving that the urinary abundance of the two peptides at m/z 1219 and m/z 1912, determined with MALDI/MS, may be considered as a possible diagnostic tool for the determination of progression toward renal failure, also with the aim of monitoring kidney function, in diabetic patients. 相似文献
248.
Kállay C Dávid A Timári S Nagy EM Sanna D Garribba E Micera G De Bona P Pappalardo G Rizzarelli E Sóvágó I 《Dalton transactions (Cambridge, England : 2003)》2011,40(38):9711-9721
The fragments of rat amylin rIAPP(17-29) (Ac-VRSSNNLGPVLPP-NH(2)), rIAPP(17-22) (Ac-VRSSNN-NH(2)), rIAPP(19-22) (Ac-SSNN-NH(2)) and rIAPP(17-20) (Ac-VRSS-NH(2)) together with the related mutant peptides (Ac-VASS-NH(2) and Ac-VRAA-NH(2)) have been synthesized and their copper(II) complexes studied by potentiometric, UV-Vis, CD and EPR spectroscopic methods. Despite the lack of any common strongly coordinating donor functions some of these fragments are able to bind copper(II) ions in the physiological pH range. The longest fragment rat amylin(17-29) keeps one equivalent copper(II) ion in solution in the whole pH range, while two other peptides Ac-VRSSNN-NH(2) and Ac-SSNN-NH(2) are also able to interact with copper(II) ions in the slightly alkaline pH range. According to the spectral parameters of the complexes, the peptides can be classified into two different categories: (i) the tetrapeptides Ac-VRSS-NH(2), Ac-VASS-NH(2) and Ac-VRAA-NH(2) can interact with copper(II) only under strongly alkaline conditions (pH > 10.0) and the formation of only one species with four amide nitrogen coordination can be detected; (ii) the peptides Ac-VRSSNNLGPVLPP-NH(2), Ac-VRSSNN-NH(2) and Ac-SSNN-NH(2) can form complexes above pH 6.0 with the major stoichiometries [CuH(-2)L], [CuH(-3)L](-) and [CuH(-4)L](2-). These data support that rIAPP(17-29) can interact with copper(II) ions under physiological conditions and the SSNN tetrapeptide fragment can be considered as the shortest sequence responsible for metal binding. Density functional theory (DFT) calculations provide some information on the possible coordination modes of Ac-SSNN-NH(2) towards the copper(II) ion and suggest that for [CuH(-2)L], [CuH(-3)L](-) and [CuH(-4)L](2-), the binding of two, three and four deprotonated amide nitrogens, with NH(-) of the side chain of asparagine as anchoring group, is probable. Moreover, these data reveal that peptides can be effective metal binding ligands even in the absence of anchoring groups, if more polar side chains are present in a specific sequence. 相似文献
249.
Zhang P Razi N Eugenio L Fentabil M Kitova EN Klassen JS Bundle DR Ng KK Ling CC 《Chemical communications (Cambridge, England)》2011,47(45):12397-12399
The structure of the pentasaccharide S259-1 in the Consortium for Functional Glycomics was investigated using a variety of techniques. Surprisingly, the structure differs from the structure assumed from the previously established specificity of the human fucosyltransferase FUT-III used in the last step of chemoenzymatic synthesis. When presented with a tetrasaccharide substrate containing both type I and type II disaccharide moieties, the enzyme generates a pentasaccharide in which the type II moiety is preferentially fucosylated. The unexpected product generated by FUT-III in this case highlights the importance of performing detailed structural analysis on products generated by enzymes. 相似文献
250.
Volatron F Heurtaux D Catala L Mathonière C Gloter A Stéphan O Repetto D Clemente-León M Coronado E Mallah T 《Chemical communications (Cambridge, England)》2011,47(7):1985-1987
Anisotropic coordination nanoparticles of the photomagnetic network Cs(I)(2)Cu(II)(7)[Mo(IV)(CN)(8)](4) are obtained through a surfactant-free high-yield synthetic procedure in water. These particles are organised as Langmuir-Blodgett films with a preferential orientation of the nano-objects within the film that exhibit a magnetic bistability below 20 K with a very large coercivity due to an efficient photo-transformation. 相似文献