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161.
Aromí G Bouwman E Burzurí E Carbonera C Krzystek J Luis F Schlegel C van Slageren J Tanase S Teat SJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(35):11158-11166
A highly asymmetric Ni(II) cluster [Ni(4)(OH)(OMe)(3)(Hphpz)(4)(MeOH)(3)](MeOH) (1) (H(2)phpz=3-methyl-5-(2-hydroxyphenyl)pyrazole) has been prepared and its structure determined by means of single-crystal X-ray diffraction by using synchrotron radiation. Variable-temperature bulk-magnetization measurements show that the complex exhibits intramolecular-ferromagnetic interactions leading to a spin ground state S=4 with close-lying excited states. Magnetization and high-frequency EPR measurements suggest the presence of sizable Ising-type magnetic anisotropy, with zero-field splitting parameters D=-0.263 cm(-1) and E=0.04 cm(-1) for the spin ground state, and an isotropic g value of 2.25. The presence of both axial and transverse anisotropy was confirmed through low-temperature specific heat determinations down to 300 mK, but no slow relaxation of the magnetization was observed by AC measurements down to 1.8 K. Interestingly, AC susceptibility measurements down to temperatures as low as 23 mK showed no indication of slow relaxation of the magnetization in 1. Thus, despite the presence of an anisotropy barrier (U approximately 4.21 cm(-1) for the purely axial limit), the magnetization relaxation remains extremely fast down to the lowest temperatures. The estimated quantum tunneling rate, Gamma>0.667 MHz, makes this complex a prime candidate for observation of coherent tunneling of the magnetization. 相似文献
162.
Haak RM Berthiol F Jerphagnon T Gayet AJ Tarabiono C Postema CP Ritleng V Pfeffer M Janssen DB Minnaard AJ Feringa BL de Vries JG 《Journal of the American Chemical Society》2008,130(41):13508-13509
The direct chemo-enzymatic DKR of racemic beta-haloalcohols is reported, yielding the corresponding optically active epoxides in a single step. The mutant haloalcohol dehalogenase HheC Cys153Ser Trp249Phe is used for the asymmetric ring closure, whereas racemization of the remaining enantiomer of the haloalcohol is achieved using the new iridacycle 3, one of the most effective racemization catalysts to date for beta-haloalcohols. 相似文献
163.
Dr. Irene Tosi Dr. Mireia Segado Centellas Dr. Elisa Campioli Dr. Alessandro Iagatti Dr. Andrea Lapini Dr. Cristina Sissa Prof. Laura Baldini Prof. Chiara Cappelli Dr. Mariangela Di Donato Prof. Francesco Sansone Dr. Fabrizio Santoro Prof. Francesca Terenziani 《Chemphyschem》2016,17(11):1686-1706
In this work, the dynamics of electronic energy transfer (EET) in bichromophoric donor–acceptor systems, obtained by functionalizing a calix[4]arene scaffold with two dyes, was experimentally and theoretically characterized. The investigated compounds are highly versatile, due to the possibility of linking the dye molecules to the cone or partial cone structure of the calix[4]arene, which directs the two active units to the same or opposite side of the scaffold, respectively. The dynamics and efficiency of the EET process between the donor and acceptor units was investigated and discussed through a combined experimental and theoretical approach, involving ultrafast pump–probe spectroscopy and density functional theory based characterization of the energetic and spectroscopic properties of the system. Our results suggest that the external medium strongly determines the particular conformation adopted by the bichromophores, with a direct effect on the extent of excitonic coupling between the dyes and hence on the dynamics of the EET process itself. 相似文献
164.
Poly‐l‐Lactic Acid Nanofiber–Polyamidoamine Hydrogel Composites: Preparation,Properties, and Preliminary Evaluation as Scaffolds for Human Pluripotent Stem Cell Culturing 下载免费PDF全文
Chiara Gualandi Nora Bloise Nicolò Mauro Paolo Ferruti Amedea Manfredi Maurilio Sampaolesi Anna Liguori Romolo Laurita Matteo Gherardi Vittorio Colombo Livia Visai Maria Letizia Focarete Elisabetta Ranucci 《Macromolecular bioscience》2016,16(10):1533-1544
Electrospun poly‐l ‐lactic acid (PLLA) nanofiber mats carrying surface amine groups, previously introduced by nitrogen atmospheric pressure nonequilibrium plasma, are embedded into aqueous solutions of oligomeric acrylamide‐end capped AGMA1, a biocompatible polyamidoamine with arg‐gly‐asp (RGD)‐reminiscent repeating units. The resultant mixture is finally cured giving PLLA‐AGMA1 hydrogel composites that absorb large amounts of water and, in the swollen state, are translucent, soft, and pliable, yet as strong as the parent PLLA mat. They do not split apart from each other when swollen in water and remain highly flexible and resistant, since the hydrogel portion is covalently grafted onto the PLLA nanofibers via the addition reaction of the surface amine groups to a part of the terminal acrylic double bonds of AGMA1 oligomers. Preliminary tested as scaffolds, the composites prove capable of maintaining short‐term undifferentiated cultures of human pluripotent stem cells in feeder‐free conditions.
165.
Mycoestrogen determination in cow milk: Magnetic solid‐phase extraction followed by liquid chromatography and tandem mass spectrometry analysis 下载免费PDF全文
Anna Laura Capriotti Chiara Cavaliere Patrizia Foglia Giorgia La Barbera Roberto Samperi Salvatore Ventura Aldo Laganà 《Journal of separation science》2016,39(24):4794-4804
Recently, magnetic solid‐phase extraction has gained interest because it presents various operational advantages over classical solid‐phase extraction. Furthermore, magnetic nanoparticles are easy to prepare, and various materials can be used in their synthesis. In the literature, there are only few studies on the determination of mycoestrogens in milk, although their carryover in milk has occurred. In this work, we wanted to develop the first (to the best of our knowledge) magnetic solid‐phase extraction protocol for six mycoestrogens from milk, followed by liquid chromatography and tandem mass spectrometry analysis. Magnetic graphitized carbon black was chosen as the adsorbent, as this carbonaceous material, which is very different from the most diffuse graphene and carbon nanotubes, had already shown selectivity towards estrogenic compounds in milk. The graphitized carbon black was decorated with Fe3O4, which was confirmed by the characterization analyses. A milk deproteinization step was avoided, using only a suitable dilution in phosphate buffer as sample pretreatment. The overall process efficiency ranged between 52 and 102%, whereas the matrix effect considered as signal suppression was below 33% for all the analytes even at the lowest spiking level. The obtained method limits of quantification were below those of other published methods that employ classical solid‐phase extraction protocols. 相似文献
166.
Niels Benedikter Vojkan Jakšić Marcello Porta Chiara Saffirio Benjamin Schlein 《纯数学与应用数学通讯》2016,69(12):2250-2303
In this paper we study the dynamics of fermionic mixed states in the mean‐field regime. We consider initial states that are close to quasi‐free states and prove that, under suitable assumptions on the initial data and on the many‐body interaction, the quantum evolution of such initial data is well approximated by a suitable quasi‐free state. In particular, we prove that the evolution of the reduced one‐particle density matrix converges, as the number of particles goes to infinity, to the solution of the time‐dependent Hartree‐Fock equation. Our result holds for all times and gives effective estimates on the rate of convergence of the many‐body dynamics towards the Hartree‐Fock evolution.© 2015 Wiley Periodicals, Inc. 相似文献
167.
168.
Jaroslav Mosná?ek Monica Bertoldo Chiara Cappelli Ivan Luká? 《Polymer Degradation and Stability》2007,92(5):849-858
Various diazo-compounds, 1,2,2,6,6-pentamethylpiperidin-4-yl diazoacetate (PMPDA), 2,2,6,6-tetramethylpiperidin-4-yl diazoacetate (TMPDA), methyl diazoacetate (MDA), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-3-methyloxycarbonylpropionate (PMPMDS), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-4-methyloxycarbonylbutanoate (PMPMDP), and one azide, methyl azidocarboxylate (MAC), were successfully prepared and grafted on polyethylene films by UV light (λ > 210 nm) activation. The treated films were characterised by FT-IR spectroscopy and contact angle measurements. Ab-initio quantum mechanical calculations allowed simulating the IR absorption spectra of the polymer grafted species. These last and the related grafting yields are discussed with reference to the diazo-compound structure and concentration. Up to 8.6 mol% of bonded groups (grafted groups/ethylene monomeric unit) were found without affecting the polymer molecular weight distribution, as shown by GPC analysis. All modified films bearing HAS groups showed very high photo-stability. 相似文献
169.
Zoccatelli G Dalla Pellegrina C Mosconi S Consolini M Veneri G Chignola R Peruffo A Rizzi C 《Electrophoresis》2007,28(3):460-466
Wheat proteinaceous alpha-amylase inhibitors (alpha-AIs) are increasingly investigated for their agronomical role as natural defence molecules of plants against the attack of insects and pests, but also for their effects on human health. The wheat genomes code for several bioactive alpha-AIs that share sequence homology, but differ in their specificity against alpha-amylases from different species and for their aggregation states. Wheat alpha-AIs are traditionally classified as belonging to the three classes of tetrameric, homodimeric and monomeric forms, each class being constituted by a number of polypeptides that display different electrophoretic mobilities. Here we describe a proteomic approach for the identification of bioactive alpha-AIs from wheat and, in particular, a 3-D technique that allows to best identify and characterize the dimeric fraction. The technique takes advantage of the thermal resistance of alpha-AIs (resistant to T > 70 degrees C) and consists in the separation of protein mixtures by 2-D polyacrylamide/starch electrophoresis under nondissociating PAGE (ND-PAGE, first dimension) and dissociating (urea-PAGE or U-PAGE second dimension) conditions, followed by in-gel spontaneous reaggregation of protein complexes and identification of the alpha-amylase inhibitory activity (antizymogram, third dimension) using enzymes from human salivary glands and from the larvae of Tenebrio molitor coleopter (yellow mealworm). Dimeric alpha-AIs from Triticum aestivum (bread wheat) were observed to exist as heterodimers. The formation of heterodimeric complexes was also confirmed by in vitro reaggregation assays carried out on RP-HPLC purified wheat dimeric alpha-AIs, and their bioactivity assayed by antizymogram analysis. The present 3-D analytical technique can be exploited for fast, full-fledged identification and characterization of wheat alpha-AIs. 相似文献
170.
Frazzoli C Dragone R Mantovani A Massimi C Campanella L 《Analytical and bioanalytical chemistry》2007,389(7-8):2185-2194
Toxicological implications of exposure to bioavailable platinum group metals, here Pd, Pt, and Rh, are still to be clarified.
This study obtained by a biosensor-based method preliminary information on potential effects on cellular metabolism as well
as on possible tolerance mechanisms. Aerobic respiration was taken as the toxicological end point to perform tandem tests,
namely functional toxicity test and tolerance test. Cells were suspended in the absence of essential constituents for growth.
The dose–response curves obtained by exposure (2 h) to the metals (nanogram per gram range) suggested the same mechanisms
of action, with Rh showing the greatest curve steepness and the lowest EC50 value. Conservative (95% lower confidence interval) EC10 values were 187, 85 and 51 ng g−1 for Pt, Pd, and Rh respectively. Tolerance patterns were tested during the same runs. The full tolerance obtained after 12 h
of exposure to each metal suggested mitochondrial inhibition of aerobic respiration as a target effect. The hazard rating
of the metals in the tolerance test changed in the Rh EC50 range, where Rh showed the lowest toxicity. The observed tolerance might suggest a protective mechanism such as metallothionein
induction at concentrations around the EC50 values. The performance of the bioassay was satisfactory, in terms of the limit of detection, repeatability, reproducibility,
roboustness, sensibility, and stability; the method’s critical uncertainty sources were identified for improvements.
Figure Respirometric curved 相似文献