TiIV-mediated reactions between primary amines and secondary carboxamides: amidine formation versus transamidation

Titanium(IV)-mediated reactions between primary amines and secondary carboxamides exhibit different outcomes, amidine formation versus transamidation, depending on the identity of the TiIV complex used and the reaction conditions employed. The present study probes the origin of this divergent behavior. We find that stoichiometric TiIV, either Cp*TiIV complexes or Ti(NMe2)4, promotes formation of amidine and oxotitanium products. Under catalytic conditions, however, the outcome depends on the identity of the TiIV complex. Competitive amidine formation and transamidation are observed with Cp*TiIV complexes, generally favoring amidine formation. In contrast, the use of catalytic Ti(NMe2)4 (< or =20 mol %) results in highly selective transamidation. The ability of TiIV to avoid irreversible formation of oxotitanium products under the latter conditions has important implications for the use of TiIV in catalytic reactions.     

Synthesis and protein degradation capacity of photoactivated enediynes

[structure: see text] The viability of proteins as targets of thermally and photoactivated enediynes has been confirmed at the molecular level. Model studies using a labeled substrate confirmed the efficacy of atom transfer from diyl radicals produced from enediynes to form captodatively stabilized carbon centered aminoacyl radicals, which then undergo either fragmentation or dimerization. To exploit this finding, a family of enediynes was developed using an intramolecular coupling strategy. Derivatives were prepared and used to target specific proteins, showing good correlation between affinity and photoinduced protein degrading activity. The findings have potential applications in the design of artificial chemical proteases and add to our understanding of the mechanism of action of the clinically important enediyne antitumor antibiotics.     

Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization

In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253–262     

Tyrosine nitration of human ERK1 introduces an intra-hydrogen bond by molecular dynamics simulations

Structural Chemistry - ERK1 is an important kinase in Ras–Raf–MEK signaling. We have recently demonstrated by mass spectrometry that Tyr210 of ERK1 can be nitrated, and the nitration...     

Synthesis of highly substituted 2,6-anti-configured tetrahydropyrans. First steps towards an efficient access to amphidinol 3 ring system

Highly functionalised and polysubstituted tetrahydropyrans, akin to the middle core of the amphidinols, can be efficiently synthesised, with full stereocontrol and in good yields, using as key steps an anti-allylation reaction coupled with an intramolecular Sakurai cyclisation. Three approaches were devised in order to reach a broad range of substitution patterns.     

LC-mass spectrometry analysis of N- and C-terminal boundary sequences of polypeptide fragments by limited proteolysis

Limited proteolysis is an important and widely used method for analyzing the tertiary structure and determining the domain boundaries of proteins. Here we describe a novel method for determining the N- and C-terminal boundary amino acid sequences of products derived from limited proteolysis using semi-specific and/or non-specific enzymes, with mass spectrometry as the only analytical tool. The core of this method is founded on the recognition that cleavage of proteins with non-specific proteases is not random, but patterned. Based on this recognition, we have the ability to determine the sequence of each proteolytic fragment by extracting a common association between data sets containing multiple potential sequences derived from two or more different mass spectral molecular weight measurements. Proteolytic product sequences derived from specific and non-specific enzymes can be accurately determined without resorting to the conventional time-consuming and laborious methods of SDS-PAGE and N-terminal sequencing analysis. Because of the sensitivity of mass spectrometry, multiple transient proteolysis intermediates can also be identified and analyzed by this method, which allows the ability to monitor the progression of proteolysis and thereby gain insight into protein structures.     

Experimental study of sensitized photooxidation reaction of compounds with anthracene structure in poly(methyl methacrylate)

Sensitized photooxidation of a series of compounds with an anthracene structure in a block poly(methyl methacrylate) (PMMA) containing a tetrapyrrole pigment (TPP) or anthraquinone dyes as spectral sensitizers, was studied. The values of changes in the molar refraction at equal to 441 and 633 nm were determined experimentally. They satisfactorily agreed with the theoretical values calculated from dispersional relationships. The initial quantum yields of the photooxidation (⁰ox) of the anthracene compounds were measured both in solution and in PMMA blocks. The lack of correlation between the ⁰ox values in the solid polymers and in the liquid solution indicates the dominating role of the polymeric matrix in determining the effectiveness of photooxidation process taking place. In the selection of the optimal polymerization conditions for the synthesis of the polymeric blocks, the values of ⁰ox of certain anthracene compounds can be up to 1. In the series of the anthraquinone dyes used, 1,4-dihydroxy and 2-aminoanthraquinones, whose ⁰ox reaches the values of 0.2–0.25 have the highest sensitizing ability.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 2, pp. 235–240, March–April, 1986.