F NMR Probes: Molecular Logic Material Implications for the Anion Discrimination and Chemodosimetric Approach for Selective Detection of HO.

Detection and discrimination of similar solvation energies of bioanalytes are vital in medical and practical applications. Currently, various advanced techniques are equipped to recognize these crucial bioanalytes. Each strategy has its own benefits and limitations.

Isolation and structure elucidation of the compounds from Teucrium hyrcanicum L. and the investigation of cytotoxicity, antioxidant activity, and protective effect on hydrogen peroxide-induced oxidative stress.

Background: Teucrium hyrcanicum L. (family Lamiaceae) is widely distributed in the North and Northwest of Iran. It has been used in the form of tea, tonic, and tincture for the treatment of various diseases such as cough, rheumatism, and fever.

Structure Elucidation of the First Sex-Inducing Pheromone of a Diatom.

Diatoms are abundant unicellular microalgae, responsible for ≈20 % of global photosynthetic CO fixation. Nevertheless, we know little about fundamental aspects of their biology, such as their sexual reproduction. Pheromone-mediated chemical communication is crucial for successful mating.

Tuneable Time Delay in the Burst Release from Oxidation-Sensitive Polymersomes Made by PISA.

Reactive polymersomes represent a versatile artificial cargo carrier system that can facilitate an immediate release in response to a specific stimulus. The herein presented oxidation-sensitive polymersomes feature a time-delayed release mechanism in an oxidative environment, which can be precisely adjusted by either tuning the membrane thickness or partial pre-oxidation. These polymeric vesicles are conveniently prepared by PISA allowing the straightforward and effective in situ encapsulation of cargo molecules, as shown for dyes and enzymes.

Total Synthesis and Bioactivity Mapping of Geodiamolide H.

The first total synthesis of the actin-stabilizing marine natural product geodiamolide H was achieved. Solid-phase based peptide assembly paired with scalable stereoselective syntheses of polyketide building blocks and an optimized esterification set the stage for investigating the key ring-closing metathesis. Geodiamolide H and synthetic analogues were characterized for their toxicity and for antiproliferative effects in cellulo, by characterising actin polymerization induction in vitro, and by docking on the F-actin target and property computation in silico, for a better understanding of structure-activity relationships (SAR).

Unravelling the dissolution mechanism of polyphosphate glasses by P NMR spectroscopy: ligand competition and reactivity of intermediate complexes.

Phosphate glass dissolution can be tailored via compositional and subsequent structural changes, which is of interest for biomedical applications such as therapeutic ion delivery. Here, solid-state P nuclear magnetic resonance characterisation of 45PO-xCaO - (55 -x)NaO glasses was correlated with dissolution studies using time-dependent liquid P NMR spectroscopy and quantitative chemical analysis. Glasses dissolved congruently in aqueous media, and the first dissolution stage was the hydration of phosphate chains.

Facile and Reliable Emission-Based Nanomolar Anion Sensing by Luminescent Iridium Receptors Featuring Chelating Halogen-Bonding Sites.

An anion sensor is presented that combines a bidentate hydrogen- (HB) or halogen-bonding (XB) site with a luminescent monocationic Ir fragment for strong binding of common anions (K up to 6×10  m ) with diagnostic emission changes. A new emission-based protocol for fast and reliable detection was derived on the basis of correction for systematic but unspecific background effects. Such a simple correction routine circumvents the hitherto practical limitations of systematic emission-based analysis of anion binding with validated open-source software (BindFit).

Caspofungin Functionalized Polymethacrylates with Antifungal Properties.

We describe the synthesis of hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PmPEGMA) and hydrophobic poly(methyl methacrylate) (PMMA) caspofungin conjugates by a post-polymerization modification of copolymers containing 10 mol % pentafluorophenyl methacrylate (PFPMA), which were obtained via reversible addition-fragmentation chain transfer copolymerization. The coupling of the clinically used antifungal caspofungin was confirmed and quantified in detail by a combination of H-, F- and diffusion-ordered NMR spectroscopy, UV-vis spectroscopy, and size exclusion chromatography. The trifunctional amine-containing antifungal was attached via several amide bonds to the hydrophobic PMMA, but sterical hindrance induced by the mPEGMA side chains prohibited intramolecular double functionalization.

Scope and Limitations of the s-Block Metal-Mediated Pudovik Reaction.

The hydrophosphorylation of phenylacetylene with di(aryl)phosphane oxides Ar P(O)H (Pudovik reaction) yields E/Z-isomer mixtures of phenylethenyl-di(aryl)phosphane oxides (1). Alkali and alkaline-earth metal di(aryl)phosphinites have been studied as catalysts for this reaction with increasing activity for the heavier s-block metals. The Pudovik reaction can only be mediated for di(aryl)phosphane oxides whereas P-bound alkyl and alcoholate substituents impede the P-H addition across alkynes.

NMR experiments on the transient interaction of the intrinsically disordered N-terminal peptide of cystathionine-β-synthase with heme.

The N-terminal segment of human cystathionine-β-synthase (CBS(1-40)) constitutes an intrinsically disordered protein stretch that transiently interacts with heme. We illustrate that the HCBCACON experimental protocol provides an efficient alternative approach for probing transient interactions of intrinsically disordered proteins with heme in situations where the applicability of the conventional [H, N]-HSQC experiment may be limited. This experiment starting with the excitation of protein side chain protons delivers information about the proline residues and thereby makes it possible to use these residues in interaction mapping experiments.

H, C, and N resonance assignments of the cytokine interleukin-36β isoform-2.

Interleukins are cytokines performing central tasks in the human immune system. Interleukin-36β (IL-36β) is a member of the interleukin-1 superfamily as are its homologues IL-36α and IL-36γ. All of them interact with a common receptor composed of IL-36R and IL-1R/acP.

Bioactive Compounds and Antioxidant Capacity of Depending on Degree of Ripeness.

Maturity stage affects the bioactive compounds as well as the antioxidant capacity in the fruit. This study was designed to identify and quantify carotenoids, as well as to evaluate vitamin E, vitamin C, antioxidant capacity and total phenolic compounds of hips at different degrees of ripeness. HPLC (high performance liquid chromatography) analysis showed different types of carotenoids at different stages of maturity of hips with significant differences ( Ë‚ 0.

N photo-CIDNP MAS NMR analysis of reaction centers of Chloracidobacterium thermophilum.

Photochemically induced dynamic nuclear polarization (photo-CIDNP) has been observed in the homodimeric, type-1 photochemical reaction centers (RCs) of the acidobacterium, Chloracidobacterium (Cab.) thermophilum, by N magic-angle spinning (MAS) solid-state NMR under continuous white-light illumination. Three light-induced emissive (negative) signals are detected.

Heme interaction of the intrinsically disordered N-terminal peptide segment of human cystathionine-β-synthase.

Cystathionine-β-synthase (CBS) belongs to a large family of pyridoxal 5'-phosphate (PLP)-dependent enzymes, responsible for the sulfur metabolism. The heme-dependent protein CBS is part of regulatory pathways also involving the gasotransmitter hydrogen sulfide. Malfunction of CBS can lead to pathologic conditions like cancer, cardiovascular and neurodegenerative disorders.

Stepwise characterization of non-synonymous mutations in the HSV-1 thymidine kinase gene by different functional assays.

Twenty amino acid substitutions in the thymidine kinase (TK) of clinical herpes simplex virus type 1 strains were assessed for conferring acyclovir (ACV) resistance. Site-directed mutagenesis, cell-free protein synthesis and protein expression in Escherichia coli were performed to obtain recombinant TK proteins, which were authenticated by Western blotting. A modified enzyme-linked immunosorbent assay (ELISA) was carried out to determine the phosphorylation activity of the mutants towards 5-bromo-2'-deoxyuridine (BrdU).

Halogen-bond-based cooperative ion-pair recognition by a crown-ether-embedded 5-iodo-1,2,3-triazole.

A crown-ether containing the iodo-triazole moiety for simultaneous cation-anion binding through Lewis-basic nitrogen atoms and C-II halogen-bond-donating iodine atoms was prepared. The complexation of the heteroditopic receptor was illustrated by X-ray and DFT analysis. The cooperative effect boosting the anion affinity was quantified by H/C NMR titration experiments.

Dual-Functional Hydrazide-Reactive and Anhydride-Containing Oligomeric Hydrogel Building Blocks.

Biomimetic hydrogels are advanced biomaterials that have been developed following different synthetic routes. Covalent postfabrication functionalization is a promising strategy to achieve efficient matrix modification decoupled of general material properties. To this end, dual-functional macromers were synthesized by free radical polymerization of maleic anhydride with diacetone acrylamide (N-(1,1-dimethyl-3-oxobutyl)acrylamide) and pentaerythritol diacrylate monostearate.

A Set of Efficient nD NMR Protocols for Resonance Assignments of Intrinsically Disordered Proteins.

The RF pulse scheme RN[N-CA HEHAHA]NH, which provides a convenient approach to the acquisition of different multidimensional chemical shift correlation NMR spectra leading to backbone resonance assignments, including those of the proline residues of intrinsically disordered proteins (IDPs), is experimentally demonstrated. Depending on the type of correlation data required, the method involves the generation of in-phase ((15) N)(x) magnetisation via different magnetisation transfer pathways such as H→N→CO→N, HA→CA→CO→N, H→N→CA→N and H→CA→N, the subsequent application of (15) N-(13) C(α) heteronuclear Hartmann-Hahn mixing over a period of ≈100 ms, chemical-shift labelling of relevant nuclei before and after the heteronuclear mixing step and amide proton detection in the acquisition dimension. It makes use of the favourable relaxation properties of IDPs and the presence of (1) JCαN and (2) JCαN couplings to achieve efficient correlation of the backbone resonances of each amino acid residue "i" with the backbone amide resonances of residues "i-1" and "i+1".