Solvation of a tetrapeptide, NAc-Ser-Phe-Val-Gly-OMe (1), in water and water/alcohol mixtures with 2,2,2-trifluoroethanol (TFE)/water or ethanol (ETH)/water has been studied by diffusion NMR intermolecular NOE measurements. The experimental results were compared those obtained from detailed Molecular Dynamics (MD) calculations. Independently, all three methods revealed preferential solvation on the surface peptide TFE water/TFE mixtures, but not ETH water/ETH mixtures. MD calculations show...

Specific interactions between molecules, including those produced by a given solute, and the surrounding solvent are essential to drive molecular recognition processes. A simple molecule such as benzene is capable of recognizing differentiating among very similar entities, methyl 2,3,4,6-tetra-O-methyl-α-d-galactopyranoside (α-Me5Gal), 2,3,4,6-tetra-O-methyl-β-d-galactopyranoside (β-Me5Gal), 1,2,3,4,6-penta-O-acetyl-β-d-galactopyranose (β-Ac5Gal), 2,3,4,6-tetra-O-methyl-α-d-mannopyranoside...

Abstract The interactions of simple carbohydrates with aromatic moieties have been investigated experimentally by NMR spectroscopy. analysis the changes in chemical shifts sugar proton signals induced upon addition entities has interpreted terms interaction geometries. Phenol and amino acids (phenylalanine, tyrosine, tryptophan) used. observed sugar–aromatic depend on nature sugar, thus stereochemistries different carbon atoms, also solvent. A preliminary study solvation state a model...

Cell-penetrating peptides (CPPs) present a versatile alternative to viral gene delivery vectors, addressing the still challenging task suitably transport desired target cell. In this work, rational design of triazole-bridged CPPs and their detailed investigation concerning peptide/lipid interactions, using also NMR-based structure calculations, are reported.

Engineered Living Materials (ELMs) combine synthetic biology with artificial materials to create biohybrid living systems capable of replicating, self-repairing, and responding external stimuli. Due their self-optimization abilities, these hold great potential for biotechnological applications. This study is a first step toward ELMs based on DNA hydrogels, focusing the production using exoelectrogenic bacterium Shewanella oneidensis. To equip functionality needed building inducible cell...

NMR allows the monitoring of molecular recognition processes in solution. Nowadays, a plethora methods are available to deduce key features interaction from both ligand or receptor points view.

Molecular mimicry is an essential part of the development drugs and molecular probes. In chemical glycobiology field, although many glycomimetics have been developed in past years, it has considered that failures their use are related to lack anomeric effects these analogues. Additionally, origin still subject virulent scientific debates. Herein, by combining synthesis, NMR methods, theoretical calculations, we show possible restore effect for acetal when replacing one oxygen atoms a CF2...

Bombesin is a tetradecapeptide that possesses random coil structure in pure water. In the presence of 30 % (v/v) 2,2,2-trifluoroethanol (TFE), it adopts partial helical conformation involving C-terminal amino acids 6–14. This conformational change, known as TFE effect, studied here terms solvation state peptide at different concentrations by means intermolecular homo- and heteronuclear NOE measurements. When an aqueous solution bombesin titrated with TFE, continual decrease water/peptide...

Abstract Homonuclear and heteronuclear intermolecular NOE measurements were applied to study the solvation of a short model tetrapeptide, NAc‐Ser‐Phe‐Val‐Gly‐OMe, dissolved in water, trifluoroethanol (TFE) mixtures both. Site specificity homonuclear NOEs between water different protons peptide was proved. Preferential by TFE water–TFE demonstrated significant decrease water–peptide interaction concomitant buildup fluorine atoms peptide. Copyright © 2001 John Wiley & Sons, Ltd.

Protein-glycosaminoglycan interactions are essential in many biological processes and human diseases, yet how their recognition occurs is poorly understood. Eosinophil cationic protein (ECP) a cytotoxic ribonuclease that interacts with glycosaminoglycans at the cell surface; this promotes destabilization of cellular membrane triggers ECP's toxic activity. To understand event differences toxicity ECP its homologues, high resolution solution structure complex between full length folded...

A short peptide throws long shadows: As revealed by NMR spectroscopy, L-Leu6, one of the shortest peptides active as a catalyst in Juliá–Colonna (JC) asymmetric epoxidation, forms stable 310-helix DMSO. The structure supports mechanistic model which N-terminus acts an oxyanion hole that interacts with β-hydroperoxyenolate intermediate JC reaction.

The effects of lysine Nε-trimethylation at selected positions the antimicrobial cecropin A−melittin hybrid peptide KWKLFKKIGAVLKVL-amide have been studied. All five monotrimethylated, four bis-trimethylated plus per-trimethylated analogues synthesized and tested for activity on Leishmania parasites Gram-positive -negative bacteria, as well hemolysis sheep erythrocytes a measure cytotoxicity. impact trimethylation solution conformation has evaluated by NMR, which indicates slight decrease in...

Abstract This revision describes an up-to-date review of our efforts to investigate the interaction carbohydrates with aromatic moieties at different levels complexity. Protein-sugar interactions have been studied using NMR experiments on a variety hevein/chitooligosaccharide systems. In addition, and computational methods also used evaluate simple entities monosaccharides. between, stacking features aromatic-containing glycomolecules described by analogous experimental-theoretical approach.

Abstract Sugar function, structure and dynamics are intricately correlated. Ring flexibility is intrinsically related to biological activity; actually plasticity in L ‐iduronic rings modulates their interactions with receptors. However, the access experimental values of energy barriers free‐energy difference for conformer interconversion water solution has been elusive. Here, a new generation fluorine‐containing glycomimetics presented. We have applied combination organic synthesis, NMR...

Cargo-peptides approaching cellular membranes: influence of cyclization and stereochemistry on translocation activity a novel group cell-penetrating peptides containing bifunctional diketopiperazine.

NMR-based metabolomics investigations of human biofluids offer great potential to uncover new biomarkers. In contrast protocols for sample collection and biobanking, procedures preparation prior NMR measurements are still heterogeneous, thus compromising the comparability resulting data. Herein, we present results an investigation handling cerebrospinal fluid (CSF) samples research. Origins commonly observed problems when conducting experiments on this type addressed, suitable experimental...

Abstract Molecular mimicry is an essential part of the development drugs and molecular probes. In chemical glycobiology field, although many glycomimetics have been developed in past years, it has considered that failures their use are related to lack anomeric effects these analogues. Additionally, origin still subject virulent scientific debates. Herein, by combining synthesis, NMR methods, theoretical calculations, we show possible restore effect for acetal when replacing one oxygen atoms...

Reaction of azaenolates 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds generally appear one tautomeric form, imino or enamino, depending on the nature chloride. The configuration enamino moiety (Z) and conformation (s-cis) compounds obtained were established by an NMR study unequivocally set nuclear Overhauser effect difference...

Cytochrome P450's (P450's) catalyze the oxidative metabolism of most drugs and toxins. Although extensive studies have proven that some demonstrate both homotropic heterotropic cooperativity toward a number substrates, mechanistic molecular details P450 allostery are still not well-established. Here, we use UV/vis heteronuclear nuclear magnetic resonance (NMR) spectroscopic techniques to study mechanism thermodynamics binding two 9-aminophenanthrene (9-AP) testosterone (TST) molecules...