Parabolic Capacity and Soft Measures for Nonlinear Equations

We first introduce, using a functional approach, the notion of capacity related to the parabolic p-Laplace operator. Then we prove a decomposition theorem for measures (in space and time) that do not charge the sets of null capacity. We apply this result to prove existence and uniqueness of renormalized solutions for nonlinear parabolic initial boundary-value problems with such measures as right-hand side.     

Bubble dispersion patterns in bubbly-flow released from a porous plug into a gas-stirred ladle

Bubbles released from a porous plug into a gas-stirred ladle present different bubbly dispersion patterns that can be studied by CFD means. Recent modeling (Alexiadis et al.) has, in fact, led to numerical results in accord with experimental data. However, due to the high number of equations involved, it is not easy to understand the physical reasons of the transitions between these patterns. In the present paper, attention was focused on the role of fragmentation and coalescence and the pattern-transition modeled by means of intersection points between these functions.     

Principal components and spatial patterns of rain over Northern Italy, in relation to wind and geopotential fields

Summary A statistical study of precipitation over the Po Valley and the Alps during four winters, based on the application of a principal component (p.c.) method, exhibited a good correlation between the first three rotated eigenvectors of the cross-product matrix (between time series of data recorded at 70 stations) and three typical atmospheric circulation schemes over Northern Italy. The study is here continued, by relating these results to meteorological fields evaluated over a region wider than the area previously considered. Our attention mainly concentrated on the fields of time trend of geopotential height at 850 hPa over Europe, between latitude 34.5 and 51 degrees North and longitudes 0 and 21 degrees East. This was suggested by some peculiar relationships shown by the statistical distributions of geopotential height and wind direction and speed with respect to the first three p.c.’s. These relationships made us think of the possibility to use those trends as predictors of precipitation fields. Our analysis puts into evidence that three spatial patterns of geopotential, height time trend can be safely associated to the first three p.c.’s and, as a consequence, to the three precipitation modes corresponding to the spatial distributions of the eigenvectors, previously identified by us. They can therefore be considered meaningful precursors of precipitation field patterns over Northern Italy and Alpine regions.

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Riassunto Uno studio statistico della precipitazione sulla pianura padana e sulle Alpi durante quattro inverni, basato sull’applicazione del metodo delle componenti principali (c.p.), ha mostrato una buona correlazione fra i primi tre autovettori rotati della matrice dei prodotti incrociati (fra le serie temporali dei dati registrati in 70 stazioni) e tre tipici schemi di circolazione atmosferica sull’Italia del Nord. Lo studio viene qui prosequito, mettendo in relazione tali risultati con campi meteorologici valutati su una zona piú ampia di quella precedentemente considerata. La nostra attenzione si è prevalentemente concentrata sui campi di tendenza temporale dell’altezza di geopotenziale a 850 hPa sull’Europa, a latitudini comprese tra 34.5 e 51 gradi Nord e longitudini fra 0 e 21 gradi Est. Ciò è stato suggerito da alcune relazioni peculiari mostrate dalle distribuzioni statistiche di altezza di geopotenziale e di direzione ed intensità del vento rispetto alle prime tre c.p., che ci hanno fatto pensare alla possibilità di usare tali tendenze come predittori del campo di precipitazione. La nostra analisi ha messo in evidenza il fatto che tre distribuzioni spaziali di tendenza temporale del campo di altezza di geopotenziale possono essere con sicurezza associate alle prime tre c.p. e., quindi, ai tre modi di precipitazione corrispondenti alle distribuzioni spaziali degli autovettori precedentemente da noi identificati. Essi possono pertanto essere considerati significativi precursori del campo di precipitazione sull’Italia del Nord e sulle regioni alpine.

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Резюме Статистическое исследование выпадения осадков над долиной реки По и Альпами в течение четырех зим, основанное на применении метода главных компонент, обнаруживает хорошую корреляцию между первыми тремя вращающимися собственными векторами матрицы векторного произведения (между временными последовательностями данных, зарегистрированных на 70 станциях) и тремя схемами типичной атмосферной циркуляции над Северной Италией. В этой работе продолжены исследования. Полученные результаты связывайотся с метеорологическими полями, вычисленными над областью, которая шире ранее рассмотренной области. Главное внимание мы обращаем на поля временного хода для геопотенциальной высоты при 850гПа над Европой, между 34.5^щ и 51^щ северной широты и между 0^щ и 21^щ восточной долготы. Это следует из специальных соотношений, полученных с помощью статистических распределений геопотенциальной высоты и направления и скорости ветра относительно первых трех главных компонент. Эти соотношения позволяют нам использовать исследованные тенденции, как предсказатели полей вьшадения осадков. Нам анализ подтверждает, что три пространственным распределения временного хода для геопотенциальной высоты могут быть связаны с первыми тремя главными компонентами и, как следствие, с тремя моделями выцадения осадков, которые соответствуют пространственным распределениям собственных векторов, ранее идентифицированных в работе [Ш]. Следовательно, они могут рассматриватяся как предвестники для распределений полей осадков над Северной Италией и над Альпами.

     

Enantioselective synthesis of preclavulone A and its methyl ester

A highly enantioselective synthesis of the (8S,12S)-enantiomer of preclavulone A and its methyl ester is described featuring the Julia protocol for installing the (Z)-double bond in the lower chain. This procedure is suitable for the preparation of labeled preclavulone analogues for biosynthetic studies on marine clavulones.     

Ion chromatography characterization of polysaccharides in ancient wall paintings

Specific programming of automated HPLC systems allows total on-line qualification, validation and stability monitoring using the concept of deferred standards. Setting up such a process for routine analyses in an automated HPLC system requires specific autosampler programming as well as specific monitoring software. With an autosampler, a double injection procedure is programmed, the first introducing the sample, and the second, a few minutes deferred, the deferred control standard. Two additional compounds are therefore added to the sample before and during the chromatographic process: the intemal standard for sample quantification and the deferred standard for system control. Specific methodologies are described of how to obtain classical quantitative analysis information as well as system qualification validation stability information. Experiments were performed to develop specified methodologies to monitor the quality of quantitative analysis during the life of the column by using the deferred standard concept to probe the effects of column ageing on separation characteristics.     

1,2-Oxopalladation versus pi-allyl palladium route. A regioconvergent approach to a key intermediate for cyclopentanoids synthesis. New insights into the Pd(II)-catalyzed lactonization reaction

Regioconvergent synthesis of the key lactone 1 from an equimolar mixture of the two olefins 4 and 5 was achieved by unique Pd(II) chemistry. The synthetic versatility of lactone 1 has been demonstrated in the synthesis of iridoids and of the endo-Corey lactone 2, which is a key intermediate for the F(2)-isoprostane synthesis. Upon exposure of the sodium salts of 4 and 5 to a catalytic amount of Pd(OAc)(2) under oxygen, in the presence of AcOH, an isomeric lactone 12 was obtained in addition to the title compound 1. The Pd(II) lactonization was optimized by fine-tuning all the factors participating in the catalytic cycle: solvent, oxidant, co-oxidant, and Pd(II) source. The Hosokawa's heterobimetallic couple emerged as the catalyst of choice. With a Cu(II)-Pd(II) couple, the redox process was transferred to copper, and the formal oxidation state of palladium remained constant during the reaction. By virtue of this new methodology, lactone 1 was obtained in a rewarding 60% yield, along with isomeric lactone 12 in 30% yield. A detailed mechanistic study was carried out in order to elucidate the formation of lactones 1 and 12. Lactone 1 was formed from either olefin 8 or olefin 10; on the other hand, lactone 12 was formed exclusively from olefin 10. An intramolecular 1,2-acyloxypalladiation was invoked for the transformation of 8 into 1, whereas the pi-allyl complexes 13 and 11 were involved in the transformation of olefin 10 into 12 and 1, respectively.     

Structural basis for recognition of bacterial cell wall teichoic acid by pseudo-symmetric SH3b-like repeats of a viral peptidoglycan hydrolase

Endolysins are bacteriophage-encoded peptidoglycan hydrolases targeting the cell wall of host bacteria via their cell wall-binding domains (CBDs). The molecular basis for selective recognition of surface carbohydrate ligands by CBDs remains elusive. Here, we describe, in atomic detail, the interaction between the Listeria phage endolysin domain CBD500 and its cell wall teichoic acid (WTA) ligands. We show that 3′O-acetylated GlcNAc residues integrated into the WTA polymer chain are the key epitope recognized by a CBD binding cavity located at the interface of tandem copies of beta-barrel, pseudo-symmetric SH3b-like repeats. This cavity consists of multiple aromatic residues making extensive interactions with two GlcNAc acetyl groups via hydrogen bonds and van der Waals contacts, while permitting the docking of the diastereomorphic ligands. Our multidisciplinary approach tackled an extremely challenging protein–glycopolymer complex and delineated a previously unknown recognition mechanism by which a phage endolysin specifically recognizes and targets WTA, suggesting an adaptable model for regulation of endolysin specificity.

Combining genetic, biochemical and computational approaches, we elucidated the molecular mechanisms underlying the recognition of Listeria wall teichoic acid by bacteriophage-encoded SH3b repeats.     

Wavelength-dependent electron and energy transfer pathways in a side-to-face ruthenium porphyrin/perylene bisimide assembly

A new side-to-face supramolecular array of chromophores, where a pyridyl-substituted perylene bisimide dye axially binds to two ruthenium porphyrin fragments, has been prepared by self-assembly. The array is formulated as DPyPBI[Ru(TPP)(CO)](2), where DPyPBI = N,N'-di(4-pyridyl)-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide and TPP = 5,10,15,20-tetraphenylporphyrin. The photophysical behavior of DPyPBI[Ru(TPP)(CO)](2) has been studied by fast (nanoseconds) and ultrafast (femtoseconds) time-resolved techniques. The observed behavior sharply changes with excitation wavelength, depending on whether the DPyPBI or Ru(TPP)(CO) units are excited. After DPyPBI excitation, the strong fluorescence typical of this unit is completely quenched, and time-resolved spectroscopy reveals the occurrence of photoinduced electron transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 5.6 ps) followed by charge recombination (tau = 270 ps). Upon excitation of the Ru(TPP)(CO) fragments, on the other hand, ultrafast (tau < 1 ps) intersystem crossing is followed by triplet energy transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 720 ps). The perylene-based triplet state decays to the ground state on a longer time scale (tau = 9.8 micros). The photophysics of this supramolecular array provides remarkable examples of (i) wavelength-dependent behavior (a small change in excitation wavelength causes a sharp switch from electron to energy transfer) and (ii) intramolecular sensitization (the triplet state of the perylene bisimide, inaccessible in the free dye, is efficiently populated in the array).     

Observation of an Unusual Molecular Switching Device. The Position of One 1,2-Dimethylimidazole Switched "On" or "Off" the Rotation of the Other 1,2-Dimethylimidazole in cis,cis,cis-Ru(II)Cl(2)(Me(2)SO)(2)(1,2-dimethylimidazole)(2)

Some cis,cis,cis-RuX(2)(Me(2)SO)(2)(1,2-Me(2)Im)L complexes [L = 1,2-Me(2)Im (1,2-dimethylimidazole) or Me(3)Bzm (1,5,6-trimethylbenzimidazole), X = Cl or Br, and Me(2)SO = S-bonded DMSO] have been synthesized and their rotamers studied in CDCl(3). From 2D NMR data, cis,cis,cis-RuCl(2)(Me(2)SO)(2)(1,2-Me(2)Im)(Me(3)Bzm) has 1,2-Me(2)Im in position "a" (cis to both Me(2)SO's and cis to "b") and Me(3)Bzm in position "b" (trans to one Me(2)SO and cis to the other). There are two stable atropisomers [head-to-tail (HT, 84%) and head-to-head (HH, 16%), defining the aromatic H of Ru-N-C-H as head for both ligands]. Me(3)Bzm has the same orientation in both atropisomers. In this orientation, the unfavorable interligand steric interactions of Me(3)Bzm with the Me(2)SO and 1,2-Me(2)Im ligands appear to be countered by favorable electrostatic attraction between the delta+ N(2)CH moiety of Me(3)Bzm and the delta- cis Cl ligands. The 1,2-Me(2)Im lacks a delta+ N(2)CH group, and its orientation is dominated by steric effects of the 2-Me group. The NMR spectrum of cis,cis,cis-RuCl(2)(Me(2)SO)(2)(1,2-Me(2)Im)(2) is consistent with four rotamers in restricted rotation about both Ru-N bonds: two HH and two HT. 2D NMR techniques (NOESY and ROESY) afforded complete proton signal assignments. The ligand disposition could be assessed from the large chemical shift dispersion of some 1,2-Me(2)Im ligand signals (Delta 0.86-1.52 ppm) arising from cis-1,2-Me(2)Im shielding modulated by deshielding influences of the cis halides. The relative stability of the four rotamers correlates best with steric interactions between the 2-Me groups and the Me(2)SO ligands. The most favorable conformer (46%) is the HH rotamer with both 2-Me groups pointing away from the Me(2)SO ligands. The least favorable conformer (14%) was also HH, but the methyl groups in this case point toward the Me(2)SO ligands. In the HT conformers of intermediate stability ( approximately 20%), one 2-Me group is toward and the other is away from the Me(2)SO ligands. The exchange cross-peaks in the 2D spectra are unusually informative about the dynamic processes in solution; the spectra provide evidence that the rotamers interchange in a definite pattern of succession. Thus, all conceivable exchange pathways are not available. 1,2-Me(2)Im "b" can rotate regardless of the orientation of 1,2-Me(2)Im "a". 1,2-Me(2)Im "a" can rotate only when "b" has the orientation with its 2-Me group directed away from "a". Thus, 1,2-Me(2)Im "b" can switch 1,2-Me(2)Im "a" rotation on or off.     

Metal-induced assembling/disassembling of fluorescent naphthalenediimide derivatives signalled by excimer emission

The new quadridentate bischelating ligands 2 and 3 display in solution the typical absorption and emission properties expected for naphthalenediimide derivatives. Spectrophotometric studies show that systems 2 and 3 interact with Zn(II), Cd(II) and Cu(I) in CHCl3 or MeCN according to an apparent 1:1 stoichiometry. Molecular modelling, ESI-MS and 1H NMR experiments indicate that the complex species formed in the presence of stoichiometric amounts of metal ion are nonhelical [2 + 2] adducts. The metal-induced self-assembling process is signalled by an intense excimer-type emission caused by the intramolecular interaction of two naphthalenediimide subunits that face each other in the [2 + 2] adduct, as shown by molecular modelling studies. In the presence of excess metal ion, a disassembling process takes place, leading to a dinuclear complex with a 2:1 metal/ligand stoichiometry, in which the intramolecular excimer is no longer allowed to form because the interaction between the naphthalenediimide subunits has been lost. Thus, the overall metal-induced assembling/disassembling process is signalled by the appearance and disappearance of the excimer band in the emission spectrum.