In this study, unique hybrid structures were constructed between a Ce-based metal-organic framework (Ce-MOF) and graphitic carbon nitride (g-C3N4) materials. addition, the g-C3N4 materials used for these heterostructures prepared by five different methods, namely conventional pyrolysis method, chemical exfoliation strong acid, activation an alkaline hydrothermal treatment, melamine-cyanuric acid supramolecular assembly with mechanochemical solvothermally pre-treated method. The structural...

We studied the co-assembly of hydrogels from a short model peptide, Fmoc-protected diphenylalanine (Fmoc-FF), in presence trivalent cations aluminium (Al) and iron (Fe). Additionally, we investigated implicit effects small molecules on self-assembly Fmoc-FF by buffering system with three commonly used buffers: HEPES, TRIS, sodium phosphate. The formation stability resulting were analyzed through rheological characterization, changes secondary structure due to addition metal monitored using...

The collapse transition of thermoresponsive dendronized polymers was characterized on a molecular scale by CW EPR spectroscopy. Aggregation the polymer is triggered dynamic structural inhomogeneities few nanometers, and dehydration chains proceeds, despite sharp phase transition, over temperature interval at least 30 °C (see picture). Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They...

The effect of several ionic liquids (ILs) on the solution structure human serum albumin (HSA) is revealed by continuous wave electron paramagnetic resonance (EPR) spectroscopy and nanoscale distance measurements with double electron−electron (DEER) spectroscopy. HSA, most abundant protein in blood, able to bind transport multiple fatty acids (FAs). Using spin-labeled FA, uptake FA their spatial distribution can be monitored. provides an indirect yet effective way characterize solution....

Intrinsically disordered proteins (IDPs) constitute a class of biologically active that lack defined tertiary and often secondary structure. The IDP Osteopontin (OPN), cytokine involved in metastasis several types cancer, is shown to simultaneously sample extended, random coil-like conformations stable, cooperatively folded conformations. By combination two magnetic resonance methods, electron paramagnetic nuclear spectroscopy, we demonstrate the OPN ensemble exhibits not only...

We present experimental evidence for the significant effect that water can have on functional structure of proteins in solution. Human (HSA) and Bovine Serum Albumin (BSA) an amino acid sequence identity 75.52% are chosen as model proteins. employ EPR-based nanoscale distance measurements using double electron-electron resonance (DEER) spectroscopy both albumins loaded with long chain fatty acids (FAs) solution to globally (yet indirectly) characterize tertiary protein structures from bound...

With the combination of molecular scale information from electron paramagnetic resonance (EPR) spectroscopy and meso-/macroscopic various other characterization techniques, formation mesoglobules thermoresponsive dendronized polymers is explained. Apparent differences in EPR spectra dependence heating rate, chemical nature dendritic substructure polymer, concentration are interpreted to be caused by a dense polymeric layer at periphery mesoglobule. This skin barrier formed narrow temperature...

Abstract This article highlights the occurrence and nature of nanoscale inhomogeneities in thermoresponsive polymers focuses on different experimental techniques for their observation characterization. Such can be regarded as nanoscopic domains collapsed polymer segments (or a small number unimers), which provide nonpolar, hydrophobic interior. Continuous wave (CW) electron paramagnetic resonance (EPR) spectroscopy amphiphilic reporter molecules (spin probes) an intrinsically local technique...

We report extended pH- and temperature-induced preparation procedures explore the materials molecular properties of human bovine serum albumin hydrogels.

The dynamic and chemical behavior of solute molecules inside new thermoresponsive hydrogels (photocrosslinked poly(N-isopropylacrylamide) (pNiPAAm) copolymers) is studied by continuous-wave electron paramagnetic resonance spectroscopy. Via addition tracer (so-called spin probes) a picture obtained the thermally induced collapse on molecular scale, which proceeds over substantially broader temperature range than indicated sharp macroscopic volume transition. sampling hydrophilic hydrophobic...

Flexible on the outside: The functional structure of transport protein in human blood, serum albumin (HSA), was characterized by distance measurements with double electron–electron resonance (DEER) spectroscopy spin-labeled fatty acids that are bound to HSA. derived has a more rigid inner core, while surface shows much greater structural flexibility. Detailed facts importance specialist readers published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

Abstract Intrinsically disordered proteins (IDPs) play crucial roles in protein interaction networks and this context frequently constitute important hubs interfaces. Here we show by a combination of NMR EPR spectroscopy that the binding cytokine osteopontin (OPN) to its natural ligand, heparin, is accompanied thermodynamically compensating structural adaptations. The core segment OPN expands upon binding. This “unfolding‐upon‐binding” governed primarily through electrostatic interactions...

Methanogenic archaea utilize a specific pathway in their metabolism, converting C1 substrates (i.e., CO2) or acetate to methane and thereby providing energy for the cell. Methyl-coenzyme M reductase (MCR) catalyzes key step process, namely methyl-coenzyme (CH3-S-CoM) plus coenzyme B (HS-CoB) CoM-S-S-CoB. The active site of MCR contains nickel porphinoid F430. We report here on coordinated ligands two paramagnetic MCRred2 states, induced when HS-CoM (a reversible competitive inhibitor) second...

Ionic liquids (ILs) feature a variety of properties that make them unique class solvents. To gain better understanding how ILs solvate compounds different chemical structure, we used pulsed high-field electron paramagnetic resonance (EPR) spectroscopy at W-band (∼94 GHz) and continuous wave EPR X-band (∼9.4 on three TEMPO-based spin probes with substitutions the 4-position: 4-R-2,2,6,6-tetramethylpiperidine-1-oxyl, R = N(CH3)3+, Cat-1, COO−, TEMPO-4-carboxylate, OH, TEMPOL. The are dissolved...

A pronounced nucleophilicity in combination with a distinct redox non‐innocence is unique feature of coordinated ligand, which the current case, leads to unprecedented carbon‐centered reactivity patterns: carbodiphosphorane‐based (CDP) pincer‐type rhodium complex allows cleave two C–Cl‐bonds geminal dichlorides via consecutive SN2‐type oxidative additions resulting formation stabilized carbene fragment. In presence suitable reductant fragment can even be converted into olefines or...

A pronounced nucleophilicity in combination with a distinct redox non‐innocence is unique feature of coordinated ligand, which the current case, leads to unprecedented carbon‐centered reactivity patterns: carbodiphosphorane‐based (CDP) pincer‐type rhodium complex allows cleave two C–Cl‐bonds geminal dichlorides via consecutive SN2‐type oxidative additions resulting formation stabilized carbene fragment. In presence suitable reductant fragment can even be converted into olefines or...

Using an electron paramagnetic resonance (EPR) spectroscopic strategy that has been developed for core-shell polymers, the complexity of binding fatty acids to human serum albumin (HSA) is characterized in detail. We unravel internal dynamics HSA solutions with by applying continuous wave EPR (CW EPR) from which we derive a consistent thermodynamic interpretation about acid interactions investigated temperature range 5 °C – 97 °C. Additionally, data CW are corroborated dynamic light...

This work focuses on the reaction mechanism of poly(sulfur nitride) ((SN)x, (S15N)x), with ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc]. We compare this IL S4N4 or its 15N labeled form S415N4, a precursor for synthesis (SN)x and (S15N)x. After purification S4N4-IL- S415N4-system via column chromatography, we characterize products 1H, 13C nuclear magnetic resonance (NMR) spectroscopy electron spray ionization time-of-flight mass spectrometry (ESI-ToF-MS). Furthermore,...

Variations in main and side chain lengths, along with the use of end groups differing nature, are often identified as key parameters influencing phase transition temperatures (cloud point temperatures) thermoresponsive polymers. Here, we systematically examine behavior poly(oligo(ethylene glycol)acrylates) respect to these three factors. Spin-probing EPR spectroscopy is employed investigate impact below at macroscopically observable thermal transition, well characterize nanoscale...

Using an electron paramagnetic resonance (EPR) spectroscopic strategy that has been developed for core–shell polymers, the complexity of binding fatty acids to human serum albumin (HSA) is characterized in detail. We unravel internal dynamics HSA solutions with by applying continuous wave EPR (CW EPR) from which we derive a consistent thermodynamic interpretation about acid interactions investigated temperature range 5–97 °C. Additionally, data CW are corroborated dynamic light scattering...

Abstract Variations in main and side chain lengths, along with the use of end groups differing natures, are often identified as key parameters influencing phase transition temperatures (cloud point temperatures) thermoresponsive polymers. Here, behavior poly(oligo(ethylene glycol)acrylates) is systematically examined respect to these three factors. Spin‐probing electron paramagnetic resonance (EPR) spectroscopy employed investigate impact below at macroscopically observable thermal...

This work focuses on the reaction mechanism of poly(sulfur nitride) ((SN)x, (S15N)x), with ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc]. We compare this IL S4N4 or its 15N-labeled form S415N4, a precursor for synthesis (SN)x and (S15N)x. After purification S4N4-IL- S415N4-IL systems via column chromatography, we characterized products 1H, 13C, 15N nuclear magnetic resonance spectroscopy electron spray ionization time-of-flight mass spectrometry. Furthermore,...