Proteomic strategies for the identification of proteinaceous binders in paintings

The identification of proteinaceous components in paintings remains a challenging task for several reasons. In addition to the minute amount of sample available, complex and variable chemical composition of the paints themselves, possible simultaneous presence of several binders and contaminants, and degradation of the original materials due to aging and pollution are complicating factors. We proposed proteomic strategies for the identification of proteins in binders of paintings that can be adapted to overcome the requirements and difficulties presented by specific samples. In particular, we worked on (1) the development of a minimally invasive method based on the direct tryptic cleavage of the sample without protein extraction; (2) the use of microwave to enhance the enzymatic digestion yield, followed by the analysis of the peptide mixtures by nanoLC-MS/MS with electrospray ionization (ESI). Moreover, as an additional tool to tackle the problem of contaminating proteins, we exploited the possibility of generating an exclusion list of the mass signals that in a first run had been fragmented and that the mass spectrometer had to ignore for fragmentation in a subsequent run. The methods, tested on model samples, allowed the identification of milk proteins in a sample from paintings attributed to Cimabue and Giotto, thirteenth-century Italian masters, decorating the vaults of the upper church in the Basilica of St. Francis in Assisi, Italy.     

X‐ray structure and density functional theory studies of an unexpected product: trans‐bis{2‐[(2‐cyanoethyl)iminomethyl]phenolato}copper(II)

The title compound, [Cu(C₁₀H₉N₂O)₂] or [Cu^II(CYMB)₂], (I), was obtained in an attempt to reduce trans‐bis(2‐{[3,5‐bis(trifluoromethyl)phenyl]iminomethyl}phenolato)copper(II), [Cu(TIMB)₂], (II), with bis(pentamethylcyclopentadienyl)cobalt(II) [decamethylcobaltocene, Cp*₂Co, (III)]. The molecular structure of (I) has the Cu^II centre located on an inversion centre of the C2/c space group. A density functional theory (DFT) analysis at the B3LYP/Lanl2dz(CuF);6‐31G**(CHNO) level performed in order to optimize the structures of the free ligands CYMB⁻ and TIMB⁻, and the metal complexes [Cu^I/II(CYMB)₂]^−/0 and [Cu^I/II(TIMB)₂]^−/0, reproduced well the X‐ray diffraction structure and allowed us to infer the insertion of the cyanomethide anion on the 3,5‐bis(trifluoromethyl)phenyl system from an evaluation of the Mulliken atomic charges and the electronic energies.     

Corrigendum to “Morita theory for coring extensions and cleft bicomodules” [Adv. Math. 209 (2) (2007) 611-648]

The results in our paper heavily rely on the journal version of [T. Brzeziński, A note on coring extensions, Ann. Univ. Ferrara Sez. VII (N.S.) 51 (2005) 15-27; a corrected version is available at http://arxiv.org/abs/math/0410020v3, Theorem 2.6]. Since it turned out recently that in the proof of the quoted theorem there are some assumptions missing, our derived results are not expected to hold at the stated level of generality either. Here we supplement the constructions in our article with the missing assumptions and show that they hold in most of our examples. In order to handle also the non-fitting case of cleft extensions by arbitrary Hopf algebroids, Morita contexts are constructed that do not necessarily correspond to coring extensions. They are used to prove a Strong Structure Theorem for cleft extensions by arbitrary Hopf algebroids. In this way we obtain in particular a corrected form of the journal version of [G. Böhm, Integral theory for Hopf algebroids, Algebr. Represent. Theory 8 (4) (2005) 563-599; Corrigendum, to be published; see also http://arxiv.org/abs/math/0403195v4, Theorem 4.2], whose original proof contains a similar error.     

Corrigendum to Cleft Extensions of Hopf Algebroids

Theorem 2.2 stated a monoidal isomorphism between the comodule categories of two bialgebroids in a Hopf algebroid. The proof of Theorem 2.2 was based on the journal version of Brzeziński (Ann Univ Ferrara Sez VII (NS) 51:15–27, 2005, Theorem 2.6), whose proof turned out to contain an unjustified step. Here we show that all other results in our paper remain valid if we drop unverified Theorem 2.2, and return to an earlier definition of a comodule of a Hopf algebroid that distinguishes between comodules of the two constituent bialgebroids.     

The L p -Solvability of the Dirichlet Problem for Planar Elliptic Equations, Sharp Results

Assume that the elliptic operator L=div (A(x)∇) is L ^p -resolutive, p>1, on the unit disc \mathbbD ì \mathbb R²\mathbb{D}\subset \mathbb {R}^{2} . This means that the Dirichlet problem

Examples of Para-cocyclic Objects Induced by BD-Laws

In a recent paper (Böhm and Stefan, Commun Math Phys 282:239–286, 2008), we gave a general construction of a para-cocyclic structure on a cosimplex, associated to a so called admissible septuple—consisting of two categories, three functors and two natural transformations, subject to compatibility relations. The main examples of such admissible septuples were induced by algebra homomorphisms. In this note we provide more general examples coming from appropriate (‘locally braided’) morphisms of monads.     

Photoinduced processes in dipyrrolyl-perfluoro-cyclopentenes

The photobehavior of five photochromic dipyrrolyl-perfluoro-cyclopentenes was studied by steady state and time-resolved absorption spectroscopy. The quantum yields of the UV-photoinduced ring-closing reaction (coloration) and the visible-stimulated cycloreversion reaction (bleaching) were measured. Kinetic and thermodynamic parameters of thermal bleaching were also determined. Nanosecond time-resolved experiments showed formation of a transient, which was not a precursor of the reaction photoproduct. This transient was tentatively assigned to a radical cation formed by direct photoionization through a short-lived triplet state. The nature of the transient species was supported by photoinduced electron transfer to electron acceptors.     

Building addressable libraries: The use of a mass spectrometry cleavable linker for monitoring reactions on a microelectrode array

Time-of-flight secondary ion mass spectrometry (TOF SIMS) has been used in conjunction with a mass spectrometry cleavable linker to determine the percent conversion of reactions that were conducted site-selectively on an addressable microelectrode array. When combined with fluorescence techniques for analysis of the reactions, the TOF SIMS experiment provides a means for optimization of both reaction confinement and reaction efficiency on the microelectrode arrays.