Isotopically Labeled Desthiobiotin Azide (isoDTB) Tags Enable Global Profiling of the Bacterial Cysteinome

Rapid development of bacterial resistance has led to an urgent need to find new druggable targets for antibiotics. In this context, residue‐specific chemoproteomic approaches enable proteome‐wide identification of binding sites for covalent inhibitors. Described here are easily synthesized isotopically labeled desthiobiotin azide (isoDTB) tags that shortened the chemoproteomic workflow and allowed an increased coverage of cysteines in bacterial systems. They were used to quantify 59 % of all cysteines in essential proteins in Staphylococcus aureus and enabled the discovery of 88 cysteines that showed high reactivity, which correlates with functional importance. Furthermore, 268 cysteines that are engaged by covalent ligands were identified. Inhibition of HMG‐CoA synthase was verified and will allow addressing the bacterial mevalonate pathway through a new target. Overall, a broad map of the bacterial cysteinome was obtained, which will facilitate the development of antibiotics with novel modes‐of‐action.     

Theoretical investigation of an acid catalyst for viable release of H2 from BN nanotubes: A local pair natural orbital coupled cluster approach

Catalytic removal of H₂ from boron-nitride (BN)-based nanomaterials at ambient conditions is of paramount importance in order to develop lightweight hydrogen storage media. Here, the DLPNO-CCSD(T) technique is used to calculate accurate relative energies and activation barriers of Brønsted acid-initiated removal of H₂ from hydrogenated BN nanotubes (HBNNTs) with six different acids. Three crucial steps are identified in the mechanism: first H₂ release, catalyst regeneration via proton transfer, and second H₂ release to ensure feasibility of the dehydrogenation proposal. Our computational studies reveal that sulfonic acids with appropriate electrophilicity can facilitate dehydrogenation of HBNNT at a low free energetic cost (∆G^‡ = 17 kcal/mol). Importantly, these findings illustrate the possibility of H₂ release from BN nanomaterials at ambient conditions and provides hope for a sustainable chemical hydrogen storage strategy.     

Exploring the interactions between buffers and cyclodextrin complexes—formation of regular inclusion or atypical non-inclusion complexes

Journal of Inclusion Phenomena and Macrocyclic Chemistry - The aim of this study was for the first time to determine the effect of 11 buffers on a γ-cyclodextrin complex, and use these and...     

Twisted Steinberg algebras

We introduce twisted Steinberg algebras over a commutative unital ring R. These generalise Steinberg algebras and are a purely algebraic analogue of Renault's twisted groupoid C*-algebras. In particular, for each ample Hausdorff groupoid G and each locally constant 2-cocycle σ on G taking values in the units $R^{\times }$, we study the algebra $A_R(G,\sigma )$ consisting of locally constant compactly supported R-valued functions on G, with convolution and involution “twisted” by σ. We also introduce a “discretised” analogue of a twist Σ over a Hausdorff étale groupoid G, and we show that there is a one-to-one correspondence between locally constant 2-cocycles on G and discrete twists over G admitting a continuous global section. Given a discrete twist Σ arising from a locally constant 2-cocycle σ on an ample Hausdorff groupoid G, we construct an associated twisted Steinberg algebra $A_R(G;\mathrm{\Sigma })$, and we show that it coincides with $A_R(G,{\sigma }^{?1})$. Given any discrete field ${\mathbb{F}}_d$, we prove a graded uniqueness theorem for $A_{{\mathbb{F}}_d}(G,\sigma )$, and under the additional hypothesis that G is effective, we prove a Cuntz–Krieger uniqueness theorem and show that simplicity of $A_{{\mathbb{F}}_d}(G,\sigma )$ is equivalent to minimality of G.     

A Self-Assembling Flavin for Visible Photooxidation

A new flavin-based gelator is reported which forms micellar structures at high pH and gels at low pH. This flavin can be used for the photooxidation of thiols under visible light, with the catalytic efficiency being linked to the self-assembled structures present.     

Nutritional and Functional Evaluation of Inula crithmoides and Mesembryanthemum nodiflorum Grown in Different Salinities for Human Consumption

The nutritional composition and productivity of halophytes is strongly related to the biotic/abiotic stress to which these extremophile salt tolerant plants are subjected during their cultivation cycle. In this study, two commercial halophyte species (Inula crithmoides and Mesembryanthemum nodiflorum) were cultivated at six levels of salinity using a soilless cultivation system. In this way, it was possible to understand the response mechanisms of these halophytes to salt stress. The relative productivity decreased from the salinities of 110 and 200 mmol L⁻¹ upwards for I. crithmoides and M. nodiflorum, respectively. Nonetheless, the nutritional profile for human consumption remained balanced. In general, I. crithmoides vitamin (B1 and B6) contents were significantly higher than those of M. nodiflorum. For both species, β-carotene and lutein were induced by salinity, possibly as a response to oxidative stress. Phenolic compounds were more abundant in plants cultivated at lower salinities, while the antioxidant activity increased as a response to salt stress. Sensory characteristics were evaluated by a panel of culinary chefs showing a preference for plants grown at the salt concentration of 350 mmol L⁻¹. In summary, salinity stress was effective in boosting important nutritional components in these species, and the soilless system promotes the sustainable and safe production of halophyte plants for human consumption.     

N–H···O=P hydrogen-bonded dimers as the main structural motif of aminophosphonate diesters

Abstract  

Crystal and molecular structures of three aminophosphonate diesters, diethyl and dibutyl [α-(quinolin-3-ylamino)-N-benzyl]phosphonates (1 and 2) and dibutyl [α-anilino-(quinolin-3-yl)methyl]phosphonate (3) were reported and comparatively discussed. Characteristic structural features for these compounds are strong N–H···O=P hydrogen bonds that connect two organophosphorus molecules in cyclic centrosymmetric dimer. Phosphoryl oxygen forms additional interaction with a C–H donor from the nearby aromatic group. Dimer formation in solution was also confirmed using electrospray ionization mass spectrometry. Mass spectra of six structurally similar aminophosphonate derivatives, 1–3 along with diethyl [α-anilino-(quinolin-3-yl)methyl]phosphonate (4), diethyl and dibutyl [α-anilino-(quinolin-2-yl)methyl]phosphonates (5 and 6) were studied and dimolecular ions [2M + Na]⁺ and [2M + H]⁺ were observed.