Electron-impact fragmentation of the bicyclo[4.1.0]heptane-2-one system: Correlations with photochemistry

The low resolution and complete high resolution mass spectra of a series of methyl and deuterium substituted bicyclo[4.1.0]heptane-2-one derivatives have been measured. An attempt has been made to test the operation of a fragmentation process analogous to the known photochemical rearrangement, and to determine if the substitution effects critical to the photorearrangement also influence the electron-impact process. The fragmentation pattern of these conjugated cyclopropyl ketones is detailed and the influence of the cyclopropyl ring is discussed. It is suggested that electron-impact-induced rearrangements which are analogous to photochemical transformations will be relatively low energy processes and will remain prominent at low ionizing voltages.     

Heterogeneous diastereoselective hydrogenation of pyridine and corresponding enamine covalently bound to pantolactone

The diastereoselective hydrogenation of 2-methyl nicotinic acid covalently bound to pantolactone was studied over supported metallic catalysts. With this chiral auxiliary, a two-steps reaction was observed with formation of tetrahydropyridine intermediate. The influence of different reaction parameters on the diastereoselectivity of the hydrogenation of pyridine and enamine substrates was studied.     

Synthesis of monodisperse polymers from proteins

Proteins are functional biopolymers; viewed as molecules, they are also monodisperse polyamides with chemically reactive side chains. This paper describes the use of proteins as starting materials for the synthesis of monodisperse polymers with nonbiological functionalities attached to the side chains. It demonstrates the complete derivatization of amine groups (lysine side chains and N-termini) on three different proteins by addition of activated carboxylate reagents in aqueous solutions containing sodium dedecyl sulfate (SDS), under denaturing conditions. Several different acylating reagents were used to generate derivatized proteins; the resulting compounds constitute a new class of monodisperse, semisynthetic polymers, having the potential for wide variation in the structure of the backbone and of the side chains. Modification of lysozyme on a gram scale demonstrated that the method can generate useful quantities of material.     

Halogenation in Fungi: What Do We Know and What Remains to Be Discovered?

In nature, living organisms produce a wide variety of specialized metabolites to perform many biological functions. Among these specialized metabolites, some carry halogen atoms on their structure, which can modify their chemical characteristics. Research into this type of molecule has focused on how organisms incorporate these atoms into specialized metabolites. Several families of enzymes have been described gathering metalloenzymes, flavoproteins, or S-adenosyl-L-methionine (SAM) enzymes that can incorporate these atoms into different types of chemical structures. However, even though the first halogenation enzyme was discovered in a fungus, this clade is still lagging behind other clades such as bacteria, where many enzymes have been discovered. This review will therefore focus on all halogenation enzymes that have been described in fungi and their associated metabolites by searching for proteins available in databases, but also by using all the available fungal genomes. In the second part of the review, the chemical diversity of halogenated molecules found in fungi will be discussed. This will allow the highlighting of halogenation mechanisms that are still unknown today, therefore, highlighting potentially new unknown halogenation enzymes.     

Early transition metal dopants in cuprous oxide: To spin or not to spin

We present a trend study of a large variety of dopants at the cation site in Cu₂O (i.e. substituting Cu), focussing largely on the early 3d-, 4d-, and 5d-transition metals (TMs) in which many of them are known to be non-magnetic. We also include s-, sp- and d¹⁰-metals for comparison. We find that doping with sp-elements results in zero spin moment while dopants with a partially filled d-band show a stronger tendency to magnetize and 3d-TM dopants exhibit a larger magnetic moment than most of the 4d- and 5d-TM dopants. From this trend study, we also find a correlation between their substitution enthalpy and associated interatomic relaxations. In particular, Ti-doped Cu₂O appears to be an interesting system, given its “peculiar” ability to exhibit a spin moment when doped with a non-magnetic substituent like Ti. We also find that the interaction between two doped Ti atoms in Ti₂:Cu₂O is predominantly antiferromagnetic, and interestingly (and unexpectedly), this interaction rapidly declines as a function of inter-dopant distance, as in the case for the magnetic late-TM dopants like Co₂:Cu₂O.     

Synthesis of the 1,2-Dihydro 1,2-Δ3−azaphosphorines

Abstract

1,2-Dihydro 1,2-Δ³? azaphosphorines were prepared by reaction of dichlorophenylphosphine with two equivalents of imines. 2-Oxo 1,2-azaphospholenes were also obtained in some cases.     

Conformation and Hydrolytic Stability of Polysaccharide from Xanthomonas campestris

Xanthomonas campestris polysaccharide in the solid state is stable to 225°C in air and 250°C in inert atmosphere. In solution, even at moderate temperatures, the polymer undergoes hydrolytic degradation via the glycosidic linkages, and occurrence of main-chain scission results in lower solution viscosity. In solution, the polymer can exist in ordered and disordered conformations. In distilled water at temperatures ≤ 50°C, the polymer exists in the disordered conformation. In the presence of salt, acid, or base the polymer exists in the ordered conformation. In the ordered conformation the polymer exhibits a far greater hydrolytic stability. The higher stability of the ordered conformation is especially demonstrated when the polymer is aged in acid or base solutions. Contrary to the expected lower stability of the glycosidic linkages in acid or base than in water, Xanthomonas campestris polysaccharide shows higher stability in these media.     

Activation energies and structural changes in carbon nanotubes during different acid treatments

In this work, we studied the effect of acid type in the final properties of CNTs as the resistance to air oxidation; for this, different techniques of characterization were used such as Raman spectroscopy, thermogravimetric analysis, and chemical analysis by ICP-AES. Through Raman spectroscopy, it is possible to monitor the structural changes induced by acids and this is reflected in changing of the activation energies for the different processes determined by thermogravimetric analysis; also by ICP-AES analysis, it was shown that the inorganic material was eliminated efficiently with the acid treatments used in this study.     

1-(1-Alkenyl)benzotriazoles: Novel α-Hydroxyacyl Anion Equivalents for the Synthesis of α-Hydroxy Ketones

α-Lithiated 1-(1-alkenyl)benzotriazoles, generated from the reactions of 1-(1-alkenyl)benzotriazoles with n-BuLi, react with a variety of electrophiles to afford α-substituted 1-(1-alkenyl)benzotriazoles which undergo epoxidation with m-CPBA followed by hydrolysis to give α-hydroxy ketones in good yields. Thus, 1-(1-alkenyl)benzotriazoles behave as α-hydroxyacyl anion equivalents.     

Exploiting Aggregation To Achieve Phase Separation in Macrocyclization

The aggregation properties of poly(ethylene glycol) (PEG) can be exploited in organic synthesis to control dilution effects. Through the use of solvent mixtures containing PEG₄₀₀/MeOH, macrocyclization by Glaser–Hay coupling can be conducted at high concentrations. The origin of the selectivity has been studied by using surface tension measurements, UV spectroscopy, and chemical tagging and demonstrates the dependence of the yield and selectivity on the aggregation of PEG₄₀₀ and its ability to preferentially solubilize organic substrates, resulting in a phase separation from the catalyst system.