Tracing active members in microbial communities by BONCAT and click chemistry-based enrichment of newly synthesized proteins.

A comprehensive understanding of microbial community dynamics is fundamental to the advancement of environmental microbiology, human health, and biotechnology. Metaproteomics, defined as the analysis of all proteins present within a microbial community, provides insights into these complex systems. Microbial adaptation and activity depend to an important extent on newly synthesized proteins (nP), however, the distinction between nP and bulk proteins is challenging.

Oligomerization of 33-mer Gliadin Peptides: Supramolecular Assemblies in Celiac Disease.

The 33-mer gliadin peptide and its deamidated derivative, known as 33-mer DGP, are proteolytically resistant peptides central to the pathomechanism of celiac disease (CeD), the autoimmune presentation of gluten-related disorders (GRD). Both peptides can form spontaneous oligomers in the nanomolar concentration, leading to the formation of nanostructures. In other protein-related diseases, oligomers and aggregates are central in their pathomechanism; therefore, it was hypothesized that the oligomerization of proteolytical-resistant 33-mer gliadin peptides could be an underrecognized disease trigger.

The value of information in predicting harmful algal blooms.

Environmental decision-making is inherently subject to uncertainty. However, decisions are often urgent, and whether to take direct action or invest in collecting additional data beforehand is pervasive. To make this trade-off explicit, the value of information (VoI) theory offers a powerful decision analytic tool to quantify the expected benefit of resolving uncertainty in a decision context.

One-pot hydroaminomethylation of an alkene under formation of primary amines by combining hydroformylation at elevated syngas pressure and biocatalytic transamination in water.

We report a novel one-pot chemoenzymatic synthesis of primary amines in water, combining rhodium-catalysed hydroformylation of styrene with a biocatalytic transamination. This process is starting from styrene at 50 mM substrate loading on a 10 mL preparative scale. Combined towards a one-pot process with both steps running concurrently, this chemoenzymatic synthesis involves a 6-DPPon/rhodium-catalysed hydroformylation of styrene at 20 bar of syngas, forming the - and -aldehydes and an enzymatic transamination of the -formed aldehydes to the corresponding primary amines catalysed by the amine transaminase from , yielding the desired primary amines with 99% conversion.

Cholesterol Conjugated Elastin-like Recombinamers: Molecular Dynamics Simulations, Conformational Changes, and Bioactivity.

Current models for elastin-like recombinamer (ELR) design struggle to predict the effects of nonprotein fused materials on polypeptide conformation and temperature-responsive properties. To address this shortage, we investigated the novel functionalization of ELRs with cholesterol (CTA). We employed GROMACS computational molecular dynamic simulations complemented with experimental evidence to validate the predictions.

Evaluation of Potency and Specificity of Cryptophycin-Loaded Antibody-Drug Conjugates.

An enhanced variant of the antimitotic toxin cryptophycin was conjugated to the anti-Her2 monoclonal antibody (mAb) Trastuzumab upon Michael addition. Either antibodies with freed hinge-region cysteines or THIOMAB formats with engineered cysteines in the mAbs light chain were added to a maleimide derivative of cryptophycin. These Antibody-Drug Conjugates (ADCs) showed retained binding to Her2 positive tumor cells and highly efficient cell killing in double-digit pM range on high Her2-expressing SK-BR-3 cells.

Transcriptomic analysis and cellular responses to nanoscale zero-valent iron in green microalga Raphidocelis subcapitata.

Nanoscale zero valent iron (nZVI) is used to remediate aquifers polluted by organochlorines or heavy metals and was also suggested to eliminate harmful algal blooms. nZVI can therefore affect microorganisms in the vicinity of the application area, including microalgae. However, studies on early transcriptomic effects of microalgae after exposure to nZVI are rare.

Annulated 1,4-Disilabenzene-1,4-diide and Dihydrogen Splitting.

The isolation of silicon analogues of phenyl anions such as (CH) and (CH) is challenging owing to their extremely high reactivity associated with their silylene character and weak C-Si π-interaction. Herein, we report the first annulated 1,4-disilabenzene-1,4-diide compound [(ADC)Si] () based on anionic dicarbene (ADC) scaffolds (ADC = PhC{N(Dipp)C}; Dipp = 2,6-PrCH) as a green-yellow crystalline solid. Compound is prepared by KC reduction of the Si(IV) chloride [(ADC)SiCl] () or the cyclic bis-chlorosilylene [(ADC)SiCl] (), which are also prepared for the first time.

The double deficiency of the SNARE proteins vti1a and vti1b affects neurite outgrowth and signaling in N1E-115 neuroblastoma cells.

During intracellular trafficking N-ethylmaleimide-sensitive-factor attachment receptor (SNARE) proteins catalyze the membrane fusion by assembling into a four-helix complex. In the mouse model, loss of the endosomal SNAREs vti1a and vti1b results in a perinatal lethal phenotype and neuronal defects including decreased neurite outgrowth in cultured primary neurons. We used a CRISPR/Cas9 system to generate a Vti1a Vti1b double knockout (DKO) in the neuroblastoma cell line N1E-115.

Proteomic Characterization of 1000 Human and Murine Neutrophils Freshly Isolated From Blood and Sites of Sterile Inflammation.

Neutrophils are indispensable for defense against pathogens. Injured tissue-infiltrated neutrophils can establish a niche of chronic inflammation and promote degeneration. Studies investigated transcriptome of single-infiltrated neutrophils which could misinterpret molecular states of these post mitotic cells.

Adducts of Lewis acidic stibanes with phosphane chalcogenides.

Starting from ClSbR (R = CF, 3,5-(CF)CH) and H(E)P(Bu) (E = O, S), we prepared the oxy- and sulphanediyl-bridged adducts RSb(Cl)-E-(H)P(Bu), which are stable against the elimination of HCl. The different electron-withdrawing substituents and chalcogen bridging units influence the size of the Sb-E-P angle. ClSb(CF) and BuSnH react to give HSb(CF), which seems to interact weakly with H(O)P(Bu) in solution as observed NMR.

Understanding the Wettability of CN (Sub)Nanopores: Implications for Porous Carbonaceous Electrodes.

Understanding how water interacts with nanopores of carbonaceous electrodes is crucial for energy storage and conversion applications. A high surface area of carbonaceous materials does not necessarily need to translate to a high electrolyte-solid interface area. Herein, we study the interaction of water with nanoporous CN materials to explain their very low specific capacitance in aqueous electrolytes despite their high surface area.

Non-Kekulé meta-Quinodimethane Singlet Diradicals Based on Classical N-Heterocyclic Carbenes.

Diradicals based on a meta-quinodimethane (m-QDM) scaffold generally have a triplet ground state and are rather scarce. Herein, m-QDM-based non-Kekulé diradicals [3,3'-(NHC)BP] (3-NHC) (NHC = SIPr = C{N(Dipp)CH}; IPr = C{N(Dipp)CH}, Me-IPr = C{N(Dipp)CMe}; Dipp = 2,6-iPrCH; BP = 1,1'-CHCH) featuring N-heterocyclic carbene (NHC) pendants are reported as crystalline solids. The EPR spectra of 3-NHC show both allowed (Δm = 1) and forbidden (Δm = 2; 'half-field') transitions characteristic for triplet diradicals.

A geminal antimony(iii)/phosphorus(iii) frustrated Lewis pair.

The geminal Lewis pair (FC)SbCHP(Bu) (1) was prepared by reacting (FC)SbCl with LiCHP(Bu). Despite its extremely electronegative pentafluoroethyl substituents, the neutral 1 exhibits a relatively soft acidic antimony function according to the HSAB concept (hard-soft acid-base). These properties lead to a reversibility in the binding of CS to 1, as observed by VT-NMR spectroscopy, while no reaction with CO is observed.

Fully Degradable Polyphosphoester Cubosomes for Sustainable Agrochemical Delivery.

Microplastic pollution and the urgent need for sustainable agriculture have raised interest in developing degradable carriers for controlled agrochemical release. Porous polymeric particles are particularly promising due to their unique release profiles compared to solid or core-shell carriers. However, creating degradable, mesoporous (2-50 nm) microparticles is challenging, and their potential for agrochemical delivery is largely unexplored.

Non-Steroidal Anti-Inflammatory Drugs Administered Intra-Articularly in Temporomandibular Joint Disorders: A Systematic Review and Meta-Analysis.

: This systematic review was designed to summarize randomized controlled trials of intra-articular administration of non-steroidal anti-inflammatory drugs (NSAIDs) for temporomandibular disorders. : Randomized controlled trials regarding intra-articular injections of non-steroidal anti-inflammatory drugs for temporomandibular disorders were included in the review. The final search was conducted on 16 June 2024 in the Bielefeld Academic Search Engine, PubMed, and Scopus databases.

Characterization of size-tuneable aescin-lipid nanoparticles as platform for stabilization of membrane proteins.

Disc-like lipid nanoparticles stabilized by saponin biosurfactants display fascinating properties, including their temperature-driven re-organization. β-Aescin, a saponin from seed extract of the horse chestnut tree, shows strong interactions with lipid membranes and has gained interest due to its beneficial therapeutic implications as well as its ability to decompose continuous lipid membranes into size-tuneable discoidal nanoparticles. Here, we characterize lipid nanoparticles formed by aescin and the phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine.

Polydentate chalcogen bonding: anion trapping with a water-stable host compound carrying Se-CF functions.

Bidentate and tetradentate chalcogen bonding host systems with SeCF functions as σ-hole donors in close proximity at the alkyne functions of 1,8-diethynylanthracene and its -dimer were prepared in quantitative yield by tin-selenium exchange reactions of the corresponding trimethylstannyl precursors with ClSeCF. The bidentate system shows chalcogen bonding interactions with THF, but does not bind halide ions. The tetradentate system cooperatively chelates chloride, bromide and iodide ions with its four CC-SeCF units by rotating the four σ-holes towards the halide ion.

A New Age of Biocatalysis Enabled by Generic Activation Modes.

Biocatalysis is currently undergoing a profound transformation. The field moves from relying on nature's chemical logic to a discipline that exploits generic activation modes, allowing for novel biocatalytic reactions and, in many instances, entirely new chemistry. Generic activation modes enable a wide range of reaction types and played a pivotal role in advancing the fields of organo- and photocatalysis.

Oxidation-dependent Lewis acidity in chalcogen adducts of Sb/P frustrated Lewis pairs.

The reactions of the frustrated Lewis pair (FC)SbCHP(Bu) with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (FC)SbCHP(E)(Bu) (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetrachloro--benzoquinone (-chloranil) gave (FC)Sb(CH)(μ-E)P(Bu)·Cat (Cat = -OCCl) with a central four-membered ring heterocycle for E = O, S, and Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of -chloranil, (FC)SbCHP(Bu)·2Cat, which is also accessible by reaction of (FC)SbCHP(Bu) with -chloranil.

Development of an efficient and scalable bioprocess for the plant hormone 12-OPDA: Overcoming the hurdles of nature's biosynthesis.

Besides its native biological function as a plant hormone, -(+)-12-oxo-phytodienoic acid (12-OPDA) serves as a metabolite for the cellular formation of (-)-jasmonic acid and has also been shown to have an influence on mammalian cells. In order to make this biologically active, but at the same time very expensive natural product 12-OPDA broadly accessible for further biological and medicinal research, we developed an efficient bioprocess based on the utilization of a tailor-made whole-cell catalyst by following the principles of its biosynthesis in nature. After process optimization, the three-step one-pot synthesis of 12-OPDA starting from readily accessible α-linolenic acid could be conducted at appropriate technically relevant substrate loadings in the range of 5-20 g L.

Overcoming a Conceptual Limitation of Industrial ε-Caprolactone Production via Chemoenzymatic Synthesis in Organic Medium.

The multi-10.000 tons scale manufactured chemical ε-caprolactone attracts high industrial interest due to its favorable biodegradability properties. However, besides being of petrochemical origin yet, its production has a conceptual limitation that is the difficult extraction of this highly water-soluble monomer from the water phase resulting from the aqueous solution of HO applied as reagent.

Enantioselective Synthesis of Secondary Amines by Combining Oxidative Rearrangement and Biocatalysis in a One-Pot Process.

This contribution describes the development of chemoenzymatic one-pot processes, which combine an oxidative rearrangement and a biotransformation catalyzed by an imine reductase (IRED), for the synthesis of highly enantiomerically enriched secondary amines, such as an aryl-substituted pyrrolidine and a benzazepine. The benefits of this chemoenzymatic one-pot approach include high overall conversions (up to >99%), high enantiomeric excesses (up to >99% ), and a straightforward synthetic approach toward secondary amines without the need to isolate the formed intermediate. For the initial chemical reaction, namely, the oxidative rearrangement, PhI(OAc) in methanol is used as a non-natural reagent, whereas the enzymatic step requires only stoichiometric amounts of d-glucose along with catalytic amounts of IRED, glucose dehydrogenase (GDH), and the cofactor NADPH.

Protein Engineering of Lipase A from Candida Antarctica to Improve Esterification of Tertiary Alcohols.

Chiral tertiary alcohols are important organic compounds in science as well as in industry. However, their preparation in enantiomerically pure form is still a challenge due to their complex structure and steric hindrances compared with primary and secondary alcohols, so kinetic resolution could be an attractive approach. Lipase A from Candida antarctica (CAL-A) has been shown to catalyze the enantioselective esterification of various tertiary alcohols with excellent enantioselectivity but low activity.