Extendable stapling of unprotected peptides by crosslinking two amines with o-phthalaldehyde

Peptide modification methods that do not rely on the cysteine residue are underdeveloped, and their development could greatly expand the current toolbox for peptide chemistry. During the course of preliminary investigations into the classical ortho-phthalaldehyde (OPA)-amine-thiol condensation reaction, we found that in the absence of thiol, OPA readily condenses with two primary alkyl amines to form a class of underexplored isoindolin-1-imine compounds under mild aqueous conditions. From the intramolecular version of this OPA-2amines reaction, an efficient and selective methodology using mild reaction conditions has been developed for stapling unprotected peptides via crosslinking of two amino groups in both an end-to-side and side-to-side fashion. The stapling method is superfast and broadly applicable for various peptide substrates with the reacting amino groups separated by a wide range of different amino acid units. The macrocyclization reactions of selected substrates are completed within 10 seconds at 5 mM concentration and within 2 minutes at 50 μM concentration. Importantly, the resulting cyclized peptides with an isoindolinimine linkage can be extended in a one-pot sequential addition manner with several different electron-deficient π electrophiles, thereby generating more complex structures.

Fluorescent Analogues of FRH Peptide: Cu(II) Binding and Interactions with ds-DNA/RNA

Four novel peptidoids, derived from the Phe-Arg-His (FRH) peptide motif, were prepared by replacing the histidine heterocycle with triazole and consequent triazole-fluorophore (coumarin) extension and also replacing arginine with less voluminous lysine. So the constructed Phe-Lys-Ala(triazole) (FKA(triazole)) peptidoids bind Cu2+ cations in water with a strong, nanomolar affinity comparable to the parent FRH and its known analogs, demonstrating that triazole can coordinate copper similarly as histidine. Moreover, even short KA(triazole)coumarin showed submicromolar affinity to Cu2+. Only FKA(triazole)coumarin with free amino groups and its shorter analog KA(triazole)coumarin showed strong induced CD spectra upon Cu2+ cation binding. Thus, KA(triazole)coumarin can be considered as the shortest peptidoid sequence with highly sensitive fluorescent and chiral CD response for Cu2+ cation, encouraging further studies with other metal cations. The FKA(triazole) coumarin peptidoids show biorelevant, 10 µM affinity to ds-DNA and ds-RNA, binding within DNA/RNA grooves. Intriguingly, only peptidoid complexes with Cu2+ strongly stabilize ds-DNA and ds-RNA against thermal denaturation, suggesting significant interactions of Cu2+ cation within the DNA/RNA binding site.

Synthesis and Characterization of Novel Uracil-Modified Chitosan as a Promising Adsorbent for Efficient Removal of Congo Red Dye

Novel Uracil-modified chitosan (UCs) adsorbent has successfully been synthesized through a four-step method during which the amino groups of chitosan have been protected, then epoxy nuclei have been incorporated, afterwards the latter have been opened using 6-amino-1,3-dimethyl uracil, and finally the amino groups have been regained via removing the protection. Its structure was checked using FTIR, XRD and SEM techniques. The adsorption capacity of UCs for anionic Congo Red (CR) dye was studied under various conditions. It decreased significantly with increasing the solution pH value and dye concentration, while increased with increasing temperature. The adsorption of UCs for CR dye at different temperatures, solution pH and dye concentrations fitted to the kinetic model of pseudo-second order and Elovich model. The intraparticle diffusion model showed that the adsorption process involves multi-step process. The isotherm of CR dye adsorption by UCs conforms to the Langmuir isotherm model indicating the monolayer nature of adsorption. The maximum monolayer coverage capacity, qmax, was 434.78 mg g−1. Studying the thermodynamic showed that the adsorption of CR dye onto UCs was endothermic as illustrated from the positive value of enthalpy (21.37 kJ mol−1). According to the values of ΔG°, the adsorption process was spontaneous at all selected temperatures. The value of ΔS° showed an increase in randomness for the adsorption of CR dye by UCs. The value of activation energy was 18.40 kJ mol−1.

Results of the complex evaluation of bryndza cheese and the byproduct milk whey with the use of enzyme MTG and its activity degree during storage

The paper examines the question of using the enzyme microbial transglutaminase (mTG) for bryndza cheese production. Microbial transglutaminase belongs to the enzyme family that catalyzes formation of bonds between amino groups. One of the problems in production of high-protein products, in particular, cheeses from goat milk is flabbiness of the clot. The use of mTG in the technological process would allow strengthening the product protein matrix, thereby improving its commercial characteristics. When performing the histological investigation of cheeses with this enzyme type to characterize the state of the protein matrix, the authors established that the product protein structure was more condensed compared to the control samples (without mTG), which affected cheese consistency. Consistency became more rubbery negatively influencing the product sensory properties, which are important traits for a consumer when buying a product. Using a Brookfield texture analyzer, it was shown that structural-mechanical characteristics were improved by 1.5 times for cheese samples produced from cow milk and by 2 times for goat cheese when mTG was used. Analysis of the enzyme catalytic activity showed that this enzyme retained its activity throughout the whole storage period, which is a potential hazard for human health. After shelf-life expiration, a change in the mTG activity was not more than 5% relative to the initial levels. The enzyme activity retained not only in cheese but also in the by-product — cheese whey, which made its processing more difficult.

4-Deoxy-l-erythro-5-hexoseulose Uronate (DEH) and DEH Reductase: Key Molecule and Enzyme for the Metabolism and Utilization of Alginate

4-Deoxy-l-erythro-5-hexoseulose uronate (DEH), DEH reductase, and alginate lyase have key roles in the metabolism of alginate, a promising carbon source in brown macroalgae for biorefinery. In contrast to the widely reviewed alginate lyase, DEH and DEH reductase have not been previously reviewed. Here, we summarize the current understanding of DEH and DEH reductase, with emphasis on (i) the non-enzymatic and enzymatic formation and structure of DEH and its reactivity to specific amino groups, (ii) the molecular identification, classification, function, and structure, as well as the structural determinants for coenzyme specificity of DEH reductase, and (iii) the significance of DEH for biorefinery. Improved understanding of this and related fields should lead to the practical utilization of alginate for biorefinery.

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

Several low molecular weight naphthoquinones are very useful in organic synthesis. These compounds have given rise to thousands of other naphthoquinones that have been tested against various microorganisms and pharmacological targets, including being used in the preparation of several drugs that are on the pharmaceutical market. Among these naphthoquinones, the series of compounds prepared from 1,2-naphthoquinone-4-sulfonic acid salts (β-NQS) stands out. In addition to being used in organic synthesis, they are excellent analytical derivatization reagents to spectrophotometrically determine drugs containing primary and secondary amino groups. This review summarizes the literature involving β-NQS.

Large interaction energy for the homodimer and the heterodimer extracted from the supramolecular chain of a bent trinuclear zinc(II) complex with a reduced Schiff base ligand

A bent trinuclear zinc complex, [Zn{ZnIL}2]•DMF {H2L = 2,2'-[(2,2-Dimethyl-1,3-propanediyl)bis(iminomethylene)]bis[6-methoxyphenol]} was synthesized and characterized by standard spectroscopic methods and X-ray diffraction analysis. The existence of coordinated amino groups and iodide counter...

Removal of Organic Compounds with an Amino Group during the Nanofiltration Process

The research covered the process of nanofiltration of low molecular weight organic compounds in aqueous solution. The article presents the results of experiments on membrane filtration of compounds containing amino groups in the aromatic ring and comparing them with the results for compounds without amino groups. The research was carried out for several commercial polymer membranes: HL, TS40, TS80, DL from various manufacturers. It has been shown that the presence of the amino group and its position in relation to the carboxyl group in the molecule affects the retention in the nanofiltration process. The research also included the oxidation products of selected pharmaceuticals. It has been shown that 4-Amino-3,5-dichlorophenol—a oxidation product of diclofenac and 4-ethylbenzaldehyde—a oxidation product of IBU, show poor separation efficiency on the selected commercial membranes, regardless of the pH value and the presence of natural organic matter (NOM). It has been shown that pre-ozonation of natural river water can improve the retention of pollutants removed.

Bimetallic PdCo Nanoparticles Loaded in Amine Modified Polyacrylonitrile Hollow Spheres as Efficient Catalysts for Formic Acid Dehydrogenation

Polyacrylonitrile hollow nanospheres (HPAN), derived from the polymerization of acrylonitrile in the presence of polystyrene emulsion (as template), were modified by surface amination with ethylenediamine (EDA), and then used as support for loading Pd or PdCo nanoparticles (NPs). The resultant bimetallic catalyst (named PdCo0.2/EDA-HPAN) can efficiently catalyze the additive-free dehydrogenation of formic acid with very high activity, selectivity and recyclability, showing turnover frequencies (TOF) of 4990 h−1 at 333 K and 915 h−1 at 303 K, respectively. The abundant surface amino groups and cyano group as well as the hollow structure of the support offer a suitable environment for achieving high dispersion of the Pd-based NPs on the surface of EDA-HPAN, thus generating ultra-small bimetallic NPs (bellow 1.0 nm) with high stability. The addition of a small portion of Co may adjust the electronic state of Pd species to a certain extent, which can further improve their capability for the dehydrogenation of formic acid. In addition, the surface amino groups may also play an important role in synergistically activating formic acid to generate formate, thus leading to efficient conversion of formic acid to hydrogen at mild conditions.