Interaction between Na+ and polymer in aqueous solution of sodium salts of poly(2-hydroxyethyl methacrylate-co-methacrylic acid) studied by 23Na-NMR

The interaction between Na⁺ and polymer was studied by ²³Na-NMR for the aqueous solution of P(HEMA-co-MAANa), sodium salt of poly(2-hydroxyethyl methacrylate-co-methacrylic acid), as a function of the polymer concentration, charge density of the polymer chain, and temperature. The NMR line width of ²³Na-NMR in 1% (w/v) aqueous solution of the P(HEMA-co-MAANa) narrowed with increasing temperature due to the rapid exchange of Na⁺ between free and polymer-bound states with a rate of exchange exceeding the quadrupolar relaxation rate in the latter state. At high concentrations of the polymer above 1.0% (w/v) at 298 K, the ²³Na-NMR relaxation fits for a single Lorentzian due to the rapid exchange between two Na⁺ states. However, it follows a biexponential decay of magnetization in dilute solutions of polymer. The biexponential decay character of relaxation increased with the increase of the fraction of the MAANa monomer unit on the polymer chain. This feature of ²³Na-NMR relaxation was used to deduce the correlation time (τ_c), the degree of binding (p_B), and the quadrupole coupling constants (X) of the polymer-bound counterion. The χ and τ_c values show that the mobilities of the polymer chain are correlated with the motion of Na⁺ in aqueous solution of the polymer and there is a small degree of the specific binding between COO^? and Na⁺. No evidence in support of the intramolecular conformational change by the charge density variation in P(HEMA-co-MAANa) was obtained. © 1993 John Wiley & Sons, Inc.     

Über den Einfluß von Temperatur und Fremdionen auf Eigenschaften und Bau der Natriumwasserglaslösungen

The Influence of Temperature and Impurities Addition on the Properties and the Constitution of Sodium Water Glass Solutions Sodium water glass (NaWG-)solutions of constant composition (SiO₂/Na₂O = 3,3; C_SiO2 = 6,2 M) and different concentration of impurities (Fe, Al, Ti, Cu, chloride, sulfate) were investigated in dependence on temperature by means of the dye absorption method, ¹H- and ²³Na-NMR spectroscopy. It is shown, that the differences in the dye absorption spectra of normalized technical NaWG-solutions, mainly depend on the Fe-concentration in the solutions and their thermal history. From the results follow a crosslinking of polymeric silicate species by Fe? O? Si bonds and/or hydrogen bridges and a fully or partially degradation of these bonds at higher temperatures (150°C).     

Temperature dependence of the interaction between water and sodium polymethacrylate in water–methanol mixture

The information for the interaction between water molecules and a polyelectrolyte was obtained from ²³Na-NMR studies for sodium polymethacrylate in water-methanol mixtures. The chemical shift and the line width of the ²³Na nucleus give the information on the immediate magnetic environment and the motion of the nucleus, respectively. The change of the chemical shift for ²³Na nucleus is investigated by decreasing the temperature and changing the mol fraction of water in the solvent. According to these results, the hydrogen bonding of water molecules and polyanions becomes weaker as the temperature of the system decreases, but the interaction increases when the temperature is below the freezing point for water in this system. This effect, due to the change of temperature, becomes higher as the water mol fraction increases in the solvent. © 1995 John Wiley & Sons, Inc.     

Coordinating Abilities Towards Sodium of Oxygenated Solvents

Tetracoordination of the sodium cation is indicated by the ²³Na-NMR. chemical shifts for NaClO₄ in binary mixtures of ether and alcohol solvents. Solvent exchange occurs by a sequential process, and involves one or several intermediates. In competition with tetrahydrofurfuryl alcohol, whereas glyme corresponds to monocyclic intermediates, diglyme and triglyme

1 For abbreviations see Table 1.

favor formation of bicyclic intermediates. The relevant conformational factors are analysed, and also serve to explain the better coordinating abilities of diglyme and triglyme, as compared to glyme. The mechanism for solvent exchange is discussed.     

13C- and Na-NMR studies of sodium octanoate in reversed micelles

The dynamic behavior of sodium octanoate (NaO), especially that of the polar headgroups of NaO, in1-hexanol in the presence of cosolubilized water was studied by Na-NMR and¹³C-NMR at 24 and 25 MHz. Na-NMR data have indicated that the mobility of the sodium ions of NaO shows the lowest value at 1.2 M of NaO at a given water content, which is related to the maximum amount of water cosolubilized into the system and the change in the structure of polar headgroups of NaO.¹³C-NMR data have shown that the mobility of methylene carbons, No. 5 and 6 of NaO, is higher than that of methylene carbons, No. 4 and 7, and that water molecules entered among the polar headgroups of NaO affect the mobility of methylene carbons of NaO, No. 5 and 6. The hydroxyl groups of1-hexanol were found to be contact with water molecules entered among the polar headgroups of NaO, and to fill the space among the hydrocarbon chains of NaO. By assuming spherical geometry the size of water pools and the average aggregation number were calculated, and the results were discussed on the basis of¹³C-NMR and Na-NMR data.     

The conformation and dynamics study of amphoteric copolymers,P(sodium 2-methacryloyloxyethanesulfonate-co-2-methacryloyloxyethyltrimethylammonium iodide), using viscometry, 14N-, and 23Na-NMR

Solution conformations and dynamic mobilities of novel amphoteric copolymers were studied for aqueous solutions of p(sodium 2-methacryloxyethanesulfonate-co-2-methacryloy-loxyethyltrimethylammonium iodide) [P(NaMES-co-METMAI)] as a function of com-position, concentration, and addition of HCI or KCI. As HCI or KCI was added successively to 5 w/v% copolymer solutions, the reduced viscosities of the solutions were reduced except the 1:1 copolymer solution. The dynamic mobility of the cationic side chain was estimated with the quadrupolar ¹⁴N-NMR relaxation technique. The motion of the interacting coun-terion, Na⁺, was studied by Poisson-Boltzmann electrostatic theories and the quadrupolar ²³Na-NMR. Since the intramolecular 1:1 ion pair between MES^- and METMA⁺ acts as an effective charge-screening factor, the copolymers P(NaMES-co-METMAI) behave as ordinary polyelectrolytes with the exception of the 1 : 1 copolymer. © 1995 John Wiley & Sons, Inc.     

Synthetic,Sodium-Ion-Conducting Tris(Macrocycle) Channels that Function in a Phospholipid Bilayer Membrane: An Overview

Abstract

A family of tris(macrocyclic) compounds of the form sidearm<N18N>C_n<N18N>C_n<N18N>sidearm, has been prepared, characterized chemically, and assayed by dynamic ²³Na-NMR for the ability to transport sodium cations in a mixed phosphatidylglycerol/phosphatidylcholine vesicle system. A number of control experiments have been conducted that reinforce the hypothesis that cation transport occurs by a channel mechanism. The tris(macrocycle) channels proved to be functional at a level of 25–50% of that found for the natural pentadecapeptide channel gramicidin. Fluorescence data confirm the expected position of the channel within the bilayer.     

Solid-state 23Na, 139La, 27Al and 29Si nuclear magnetic resonance spectroscopic investigations of cation location and migration in zeolites LaNaY

²³Na Magic-angle spinning (MAS), double rotation (DOR) and two-dimensional nutation nuclear magnetic resonance (NMR) and static ¹³⁹La NMR spectroscopy were applied to study the location and migration of sodium and lanthanum cations in faujasites. Generally, ²³Na MAS NMR spectroscopy of as-exchanged and hydrated zeolites LaNaY was used for the quantitative determination of non-localized Na⁺ in the large cavities at a ²³Na NMR shift of −9 ppm and of sodium cations observed at −13 ppm. The latter originate from Na⁺ ions located on position SII in the large cavities, on position SI in the hexagonal prisms and on positions SII′ and/or SI′ in the sodalite cages. The ²³Na MAS NMR signal at about −13 ppm was found to be caused by two coonents. The component that is characterized by a quadrupolar interaction causing a field-dependent shift and a signal at v₁ = 2v_rf in the two-dimensional quadrupolar nutation spectra is attributed to Na⁺ enclosed in the sodalite cages. The ²³Na MAS NMR spectra of dehydrated lanthanum-exchanged faujasites are characterized by a low-field Gaussian line of Na⁺ located on SI positions in the hexagonal prisms and a high-field quadrupole pattern of Na⁺ located on positions SII and SI′. The migration of lanthanum cations from the large cavities to position SI′ in the sodalite cages was monitored by ¹³⁹La NMR spectroscopy and verified by a theoretical estimation of the electric field gradient. The lanthanum migration was found to be coupled with a strain of SiOT and AlOT angles observed by ²⁹Si and ²⁷Al MAS NMR high-field shifts, respectively.     

XANES and XPS characterization of hard amorphous CSixNy thin films grown by RF nitrogen plasma assisted pulsed laser deposition

Amorphous carbon silicon nitride thin films were grown on (100) oriented silicon substrates by pulsed laser deposition (PLD) assisted by an RF nitrogen plasma source. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the hard amorphous thin films by XPS in dependence on the composition of the mixed graphite / Si₃N₄ PLD target. The universal nanohardness was measured to be at maximum load force of 0.1 mN up to 23 GPa for thin CSi_xN_y films with reference value of 14 GPa for single crystalline silicon. X-ray photoelectron spectroscopy (XPS) of CSi_xN_y film surfaces showed a clear correlation of binding energy and intensity of fitted features of N 1s, C 1s, and Si 2p peaks to the composition of the graphite / Si₃N₄ target and to nitrogen flow through the plasma source, indicating soft changes of binding structure of the thin films due to variation of PLD parameters. Auger electron spectroscopy (AES) of Si KL₂₃L₂₃;¹D Auger transition gave a detailed view of bonding structure of Si in the CSi_xN_y films. The intensity of π* and σ* resonances at the carbon K-edge X-ray absorption near-edge structure (XANES) of the CSi_xN_y films measured at BESSY I corresponded to the nanohardness of the CSi_xN_y films, thus giving insight into chemical binding structure of superhard amorphous materials.     

Competitive binding exchange between alkali metal ions (K+, Rb+, and Cs+) and Na+ ions bound to the dimeric quadruplex [d(G4T4G4)]2: a 23Na and 1H NMR study

A comparative study of the competitive cation exchange between the alkali metal ions K⁺, Rb⁺, and Cs⁺ and the Na⁺ ions bound to the dimeric quadruplex [d(G₄T₄G₄)]₂ was performed in aqueous solution by a combined use of the ²³Na and ¹H NMR spectroscopy. The titration data confirm the different binding affinities of these ions for the G‐quadruplex and, in particular, major differences in the behavior of Cs⁺ as compared to the other ions were found. Accordingly, Cs⁺ competes with Na⁺ only for the binding sites at the quadruplex surface (primarily phosphate groups), while K⁺ and Rb⁺ are also able to replace sodium ions located inside the quadruplex. Furthermore, the ¹H NMR results relative to the CsCl titration evidence a close approach of Cs⁺ ions to the phosphate groups in the narrow groove of [d(G₄T₄G₄)]₂. Based on a three‐site exchange model, the ²³Na NMR relaxation data lead to an estimate of the relative binding affinity of Cs⁺ versus Na⁺ for the quadruplex surface of 0.5 at 298 K. Comparing this value to those reported in the literature for the surface of the G‐quadruplex formed by 5′‐guanosinemonophosphate and for the surface of double‐helical DNA suggests that topology factors may have an important influence on the cation affinity for the phosphate groups on DNA. Copyright © 2009 John Wiley & Sons, Ltd.     

The Synthesis of Novel Macrocycles,Part V. The Coumarin Crown Ethers and Cation Binding with Fluorescence Spectra

Abstract

The 4-H, 4-methyl and 4-phenyl derivatives of benzo-α-pyrone of 12-crown-4 and 15-crown-5 were synthesised starting from 4-substituted-6,7-dihydroxy- and 7,8-dihydroxybenzo-α-pyrones which reacted with dichloropolyethylene glycols in DMF/water/alkali carbonate. The coumarin-macrocycles were identified by elemental analysis, IR, EI-GC-MS as well as ¹H, ¹³C NMR spectroscopy. The full experimental and spectral data is reported along with ion binding data studied in acetonitrile using fluorescence spectroscopy. The binding of the fluorogenic coumarin-crowns with Li⁺, Na⁺ and K⁺ were recognized as specific alterations on their fluorescence spectra that strongly originated from the structures. The observed CEQFS depending on the bound cation radii and macrocycle size evidenced the rules of cationic recognition of macrocycles. Some 15-crown-5 derivatives exhibited interesting Li⁺ and Na⁺ binding selectivities.     

Spectroscopic studies on binding of Puerarin to human serum albumin

The interaction between Puerarin with human serum albumin has been studied for the first time by spectroscopic methods including fluorescence quenching technology, circular dichroism (CD) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy under simulative physiological conditions. The results of fluorescence titration revealed that Puerarin can strongly quench the intrinsic fluorescence of HSA by static quenching and there is a single class of binding site on HSA. In addition, the studies of CD spectroscopy and FT-IR spectroscopy showed that the binding of Puerarin to HSA changed slightly molecular conformation of HSA. Furthermore, the thermodynamic functions ΔH⁰ and ΔS⁰ for the reaction were calculated to be −9.067 kJ mol⁻¹ and 54.315 J mol⁻¹ K⁻¹ according to van’t Hoff equation. These data suggested that both hydrogen bond and hydrophobic interaction play a major role in the binding of Puerarin to HSA, which is in good agreement with the result of molecular modeling study.     

Conformational Analysis of the cis- and trans-Isomers of FK506 by NMR and Molecular Dynamics

The potent immunosuppressant drug FK506 ( 2 ) has been examined by ¹H- and ¹³C-NMR spectroscopy and NOE-restrained molecular dynamics to elucidate the conformation in solution. A combination of two- and three-dimensional NMR techniques was used to completely assign the ¹H- and ¹³C-NMR chemical shifts of the two configurational isomers resulting from the cis-trans isomerization about the single amide bond. Hetero- and homonuclear coupling constants were measured to assign the diastereotopic methylene protons at C(16), C(18), and C(23). Intramolecular H? H distances were defined from NOESY spectra recorded at ?30° in CDCl₃ and used as constraints in molecular-dynamics simulations. The conformational preferences of 2 in solution are discussed in light of the constitutional features recently proposed to be necessary for binding and activity.     

Counterion binding in Na poly(acrylate) gel. An 23Na‐NMR study

Counterion binding in Na poly(acrylate) gel immersed in water/organic solvent [ethanol (EtOH), acetonitrile (AcN), or tetrahydrofuran (THF)] mixtures was investigated by ²³Na‐NMR spectroscopy. With an increase in the content of an organic solvent (～40–50 vol %), the ²³Na chemical shift significantly moved downfield on a gel collapse. This downfield shift strongly suggests that the gel collapse was induced by contact ion‐pair formation between the counterion and the carboxyl anion on the polymer. With a further increase in the solvent content (～90 vol %), the chemical shift for an EtOH system showed a slight upfield shift, while THF and AcN systems maintained downfield shifts. The contrasting behaviors for EtOH and the latter two solvent systems were interpreted as being caused by desolvation and resolvation of bound Na⁺ counterions because of deswelling and reswelling of the respective gels in the pertinent solvent concentration regions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4412–4420, 2004     

具有抗HIV病毒活性的杂多酸HPA-23与谷胱甘肽的作用

以谷胱甘肽作为病毒包络蛋白的模拟物，用ＮＭＲ方法研究了与具有抗爱滋病病毒活性杂多酸ＨＰＡ－２３的作用。对不同配比的ＨＰＡ－２３和谷胱甘肽混合物的＾１Ｈ和＾１＾８＾３ＷＮＭＲ谱研究结果表明，还原型和氧化型谷胱甘肽均以Ｃ末端ＣＯＯ＾－与ＨＰＡ－２３骨架的钨原子配位，还原型谷胱甘肽侧链上的巯基（ＳＨ）也参加配位。ＣＯＳＹ谱证明了ＳＨ配位为慢交换反应。早在七十年代初，人们就发现杂多酸具有抗病毒活性。最近报     

Direct Observation of Ca2+‐Induced Calmodulin Conformational Transitions in Intact Xenopus laevis Oocytes by 19F NMR Spectroscopy

The Ca²⁺‐mediated conformational transition of the protein calmodulin (CaM) is essential to a variety of signal transduction pathways. Whether the transition in living cells is similar to that observed in buffer is not known. Here, we report the direct observation by ¹⁹F NMR spectroscopy of the transition of the Ca²⁺‐free and ‐bound forms in Xenopus laevis oocytes at different Ca²⁺ levels. We find that the Ca²⁺‐bound CaM population increased greatly upon binding the target protein myosin light‐chain kinase (MLCK) at the same Ca²⁺ level. Paramagnetic NMR spectroscopy was also exploited for the first time to obtain long‐range structural constraints in cells. Our study shows that ¹⁹F NMR spectroscopy can be used to obtain long‐range structural constraints in living eukaryotic cells and paves the way for quantification of protein binding constants.     

Fluorescence quenching of triazatruxene-based glycocluster induced by peanut agglutinin lectin

A novel triazatruxene-based fluorescent glycocluster was synthesized and its selective binding interactions with PNA lectin were investigated by fluorescence spectroscopy,CD spectroscopy,and a turbidity assay.The glycocluster exhibited a strong binding affinity for PNA lectin with a Stern-Volmer quenching constant of 5.8×10⁵ mol^-1L     

The Synthesis of Novel Crown Ethers, Part VII [1]. Coumarin Derivatives of Benzocrowns and Cation Binding from Fluorescence Spectra

4-[3-(1-benzopyran-2-one)] derivativesof benzo[12]crown-4, benzo[15]crown-5 andbenzo-[18]crown-6 were synthesized from4-[3-(1-benzopyran-2-one)]-1,2-dihydroxy-benzenereacting with bis-ethyleneglycol dihalides orpentaethylene glycol ditosylate in alkali carbonate/DMF/water. The original products were identified byhigh resolution EI-mass spectra as well as IR,¹H-NMR and ¹³C-NMR spectroscopy. The 1 : 1binding constants of Mg²⁺, Li⁺, Na⁺ andK⁺ with the coumarin-benzocrowns were estimated usingfluorescence emission spectroscopy in acetonitrile.The complexing enhanced quenching fluorescence spectra(CEQFS) and complexing enhanced fluorescence spectra(CEFS) exhibited the ion binding powers due tocationic recognition rules of the macrocycles.     

Fluorinated Carbohydrates as Lectin Ligands: Dissecting Glycan–Cyanovirin Interactions by Using 19F NMR Spectroscopy

NMR spectroscopy and isothermal titration calorimetry (ITC) are powerful methods to investigate ligand–protein interactions. Here, we present a versatile and sensitive fluorine NMR spectroscopic approach that exploits the ¹⁹F nucleus of ¹⁹F‐labeled carbohydrates as a sensor to study glycan binding to lectins. Our approach is illustrated with the 11 kDa Cyanovirin‐N, a mannose binding anti‐HIV lectin. Two fluoro‐deoxy sugar derivatives, methyl 2‐deoxy‐2‐fluoro‐α‐D ‐mannopyranosyl‐(1→2)‐α‐D ‐mannopyranoside and methyl 2‐deoxy‐2‐fluoro‐α‐D ‐mannopyranosyl‐(1→2)‐α‐D ‐mannopyranosyl‐(1→2)‐α‐D ‐mannopyranoside were utilized. Binding was studied by ¹⁹F NMR spectroscopy of the ligand and ¹H–¹⁵N HSQC NMR spectroscopy of the protein. The NMR data agree well with those obtained from the equivalent reciprocal and direct ITC titrations. Our study shows that the strategic design of fluorinated ligands and fluorine NMR spectroscopy for ligand screening holds great promise for easy and fast identification of glycan binding, as well as for their use in reporting structural and/or electronic perturbations that ensue upon interaction with a cognate lectin.