An efficient diastereoselective route to differentially protected anti-4-amino-1-alken-3-ols

Zinc-promoted hydroxyallylation of alpha-amidoalkyl arylsulfones 4 using 3-bromo-propenyl methyl carbonate 5 proceeds smoothly in DMF at room temperature to afford high yields of differentially protected anti-1,2-amino alcohols 6.     

Di-n-octyltin(IV) complexes with 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acid: Syntheses and assessment of solid state structures by Sn Mössbauer and X-ray diffraction and further insight into the solution structures using electrospray ionization MS, Sn NMR and variable temperature NMR spectroscopy

Reactions of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids (LHH′, where the aryl group is an R-substituted phenyl ring such that for L¹HH′: X = H; L²HH′: X=2′-OCH₃; L³HH′: X = 3′-CH₃; L⁴HH′: X = 4′-CH₃; L⁵HH′:X = 4′-Cl) with ⁿOct₂SnO in 2:1 and 1:1 molar ratios have been investigated. Two types of complexes, ⁿOct₂Sn(LH)₂ and {[ⁿOct₂Sn(LH)]₂O}₂, were isolated and they have been characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS, IR and ^119mSn Mössbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of ⁿOct₂Sn(L¹H)₂ (1), {[ⁿOct₂Sn(L²H)]₂O}₂ (3) and {[ⁿOct₂Sn(L³H)]₂O}₂(4) were determined. The mononuclear complex 1 was found to adopt a skew-trapezoidal bipyramidal arrangement around the tin atom while 3 and 4 are centrosymmetric tetranuclear bis(dicarboxylatotetrabutyldistannoxane) complexes containing a planar Sn₄O₂ core in which two μ₃-oxo O-atoms connect an Sn₂O₂ ring to two exocyclic Sn-atoms. The solution structures were confirmed by ¹¹⁹Sn NMR spectroscopy by observing one tin resonance in compound 1 and two tin resonances in {[ⁿOct₂Sn(L⁵H)]₂O}₂ (5). {[ⁿOct₂Sn(L²H)]₂O}₂ (3) and {[ⁿOct₂Sn(L³H)]₂O}₂ (4) undergo very complex exchange processes in deuteriochloroform solution, which has been confirmed by variable temperature ¹H NMR spectroscopy. The cleavage of the most labile bond in the molecule was studied by ESI mass spectrometry.     

Determination of twenty-five elements in lichens by sector field inductively coupled plasma mass spectrometry and microwave-assisted acid digestion

A simple and efficient digestion method for rapid sample preparation and quantification of 25 chemical elements in lichens by sector field inductively coupled plasma mass spectrometry is described. A microwave (MW)-assisted acid digestion was carried out at atmospheric pressure simultaneously handling up to 80 samples in screw-capped disposable polystyrene tubes. This digestion procedure was compared with the established MW digestion in closed vessels in order to examine its potential applicability in routine analysis for environmental monitoring. Three certified reference materials, i.e. BCR 482 (lichens), BCR 62 (olive leaves) and BCR 100 (beech leaves), as well as a small set of real samples were analyzed. Limits of quantification, accuracy and precision of the method were assessed. The majority of the elements were totally recovered from the lichens and from the other vegetable matrices. Low contamination risk, simplicity, time-saving, and applicability in routine analyses make this method very suitable for use in extensive screening campaigns.     

Theoretical and spectroscopic study of nickel(II) porphyrin derivatives

A set of substituted (sulfonate, amino) nickel porphyrin derivatives such as phthalocyanine and phenylporphyrin was studied by spectroscopic (UV-vis, FTIR, XPS) and quantum-chemical methods. The Q and Soret bands were identified in the UV-vis spectra of aquo solutions of the tetrasulfo-substituted complexes and in DMF and ACN solutions of the amino-substituted phenylporphyrin and phthalocyanine Ni(II) complexes, respectively. In all the complexes the frontier molecular orbitals predict that the oxidation and reduction sites are localized on the ligand rather than in the metal atom. A natural bonding orbital (NBO) analysis of all the complexes showed that a two-center bond NBO between the pyrrolic nitrogens (Npyrr) and the nickel atom does not exist, the Npyrr...Ni interaction occurring instead by a delocalization from one lone pair of each Npyrr toward one lone pair of the nickel atom, as estimated by second-order perturbation theory. The calculated values of electronic transitions between the frontier molecular orbitals are in good agreeement with the UV-vis data. At the theoretical level, we found that while the ligand effect is more important in the Q-band (approximately 16 kcal/mol), the substituent effect is more significant in the Soret band (approximately 9 kcal/mol). A good agreement was also found between the experimental and calculated infrared spectra, which allowed the assignment of many experimental bands. The XPS results indicate that the Ni(II) present in the phenylporphyrin structure is not affected by a change of the substituent (sulfonate or amino).     

Pyrene-Terminated Tin Sulfide Clusters: Optical Properties and Deposition on a Metal Surface

Herein, we present the synthesis of two pyrene-functionalized clusters, [(R^pyrSn)₄S₆]⋅2 CH₂Cl₂ ( 4 ) and [(R^pyrSn)₄Sn₂S₁₀]⋅n CH₂Cl₂ (n=4, 5 a ; n=2, 5 b ; R^pyr=CMe₂CH₂C(Me)N-NC(H)C₁₆H₉), both of which form in reactions of the organotin sulfide cluster [(R^NSn)₄S₆] ( C ; R^N=CMe₂CH₂C(Me)N-NH₂) with the well-known fluorescent dye 1-pyrenecarboxaldehyde ( B ). In contrast, reactions using an organotin sulfide cluster with another core structure, [(R^NSn)₃S₄Cl] ( A ), leads to formation of small molecular fragments, [(R^pyrCl₂Sn)₂S] ( 1 ), (pyren-1-ylmethylene)hydrazine ( 2 ), and 1,2-bis(pyren-1-ylmethylene)hydrazine ( 3 ). Besides synthesis and structures of the new compounds, we report the influence of the inorganic core on the optical properties of the dye, which was analyzed exemplarily for compound 5 a via absorption and fluorescence spectroscopy. This cluster was also used for exploring the potential of such non-volatile clusters for deposition on a metal surface under vacuum conditions.     

Asymptotic results for finite superpositions of Ornstein–Uhlenbeck processes

A model of intermittency based on superposition of Lévy driven Ornstein–Uhlenbeck processes is studied in [6 Grahovac, D., Leonenko, N., Sikorskii, A., and Te?niak, I. 2016. Intermittency of superpositions of Ornstein–Uhlenbeck type processes. J. Stat. Phys. 165:390–408.[Crossref], [Web of Science ®] , [Google Scholar]]. In particular, as shown in Theorem 5.1 in that paper, finite superpositions obey a (sample path) central limit theorem under suitable hypotheses. In this paper we prove large (and moderate) deviation results associated with this central limit theorem.     

A Novel MS-Cleavable Azo Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS)

The chemical cross-linking/mass spectrometry (MS) approach is a growing research field in structural proteomics that allows gaining insights into protein conformations. It relies on creating distance constraints between cross-linked amino acid side chains that can further be used to derive protein structures. Currently, the most urgent task for designing novel cross-linking principles is an unambiguous and automated assignment of the created cross-linked products. Here, we introduce the homobifunctional, amine-reactive, and water soluble cross-linker azobisimidoester (ABI) as a prototype of a novel class of cross-linkers. The ABI-linker possesses an innovative modular scaffold combining the benefits of collisional activation lability with open shell chemistry. This MS-cleavable cross-linker can be efficiently operated via free radical initiated peptide sequencing (FRIPS) in positive ionization mode. Our proof-of-principle study challenges the gas phase behavior of the ABI-linker for the three amino acids, lysine, leucine, and isoleucine, as well as the model peptide thymopentin. The isomeric amino acids leucine and isoleucine could be discriminated by their characteristic side chain fragments. Collisional activation experiments were conducted via positive electrospray ionization (ESI) on two Orbitrap mass spectrometers. The ABI-mediated formation of odd electron product ions in MS/MS and MS³ experiments was evaluated and compared with a previously described azo-based cross-linker. All cross-linked products were amenable to automated analysis by the MeroX software, underlining the future potential of the ABI-linker for structural proteomics studies.

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Closure,Defeasibility and Conclusive Reasons

It is argued, on the basis of new counterexamples, that neither knowledge nor epistemic justification (or “epistemic rationality”) can reasonably be thought to be closed under logical implication. The argument includes an attempt to reconcile the fundamental intuitions of the opposing parties in the debate.

On the rationality of moduli spaces of pointed curves

Motivated by several recent results on the geometry of the modulispaces of stable curves of genus g with n marked points, we determine the birational structureof these spaces for small values of g and n by exploiting suitableplane models of a general curve. More precisely, _g,n is shownto be rational for g = 2 and 1 n 12, g = 3 and 1 n 14, g= 4 and 1 n 15, and g = 5 and 1 n 12     

Stable bundles and the first eigenvalue of the Laplacian

In this article we study the first eigenvalue of the Laplacian on a compact manifold using stable bundles and balanced bases. Our main result is the following: Let M be a compact Kähler manifold of complex dimension n and E a holomorphic vector bundle of rank r over M. If E is globally generated and its Gieseker point T_e is stable, then for any Kähler metric g on M\(\lambda _1 (M,g) \leqslant \frac{{4\pi h^0 (E)}}{{r(h^0 (E) - r)}} \cdot \frac{{\left\langle {C_1 (E) \cup [\omega ]^{n - 1} ,[M]} \right\rangle }}{{(n - 1)!vol(M,[\omega ])}}\) where ω = ω_g is the Kähler form associated to g.By this method we obtain, for example, a sharp upper bound for λ₁ of Kähler metrics on complex Grassmannians.