Thermodynamic and kinetic characterization of host-guest association between bolaform surfactants and alpha- and beta-cyclodextrins

The thermodynamics and kinetics of formation of host-guest complexes between a series of bolaform surfactants of type C n Me 6 (2+)2Br (-) ( n = 8, 10, and 12) and alpha-cyclodextrin and beta-cyclodextrin were studied with the aid of isothermal titration calorimetry (ITC) at 298.15 and 308.20 K. The association constant, the enthalpy, and the entropy of formation were determined. The obtained thermodynamic parameters are compared with parameters for the micelle formation of a related cationic surfactant. The difference in magnitude and sign between the parameters of the alpha-CD and beta-CD complexes is discussed based on the curvature of the cavity of the CD. We suggest that the water molecules inside the alpha-CD cavity are not able to maintain their hydrogen bond network. Upon complex formation these water molecules are expelled and reform their hydrogen bond network. The situation is different in the larger beta-CD cavity where water has the possibility of a more extensive hydrogen bonding. The kinetics for alpha-CD is slow, associated with high activation energies for both association and dissociation of the complex. The rates increased with a decrease in the number of methylene groups in the hydrocarbon chain. The slow kinetics is argued to originate from the fact that the charged headgroup needs to be pushed through a relative nonpolar cavity. A comparison is made with the Born energy.     

Electronic properties of small platinum particles as seen by NMR

No doubt partially because of their catalytic activity, small platinum particles on mineral supports have been extensively studied by NMR during recent years. Here we will discuss these data in relation to the expected electronic properties of small metal particles. Experimentally, no quantum size effects are found, but the local densities of state at the Fermi energy show considerable site-dependence when going from the surface to the interior of the particle. Such effects have been theoretically predicted for an infinite film.     

NMR measurement of self-diffusion coefficients by slice selection

Most of the time, so-called inversion-recovery experiments concern longitudinal nuclear magnetization of the whole sample, the region of interest being limited by the transmitting-receiving coil. Here we address the question of what occurs if the region of interest is purposely limited to a thin slice selected by means of procedures employing magnetic field gradients. Gradients of both magnetic fields (B(0), the static magnetic field, and B(1), the radio-frequency magnetic field) can be used. In this study we resorted essentially to B(1) gradients and novel procedures, based on the natural inhomogeneity of the B(1) field delivered by a saddle coil, are described. It is obvious that molecules leaving and entering the slice during the evolution (recovery) period should influence the magnetization recovery. Molecular self-diffusion is responsible for such effects, experimentally visible and accounted for by an appropriate theory which has been approximated for by permitting an easy physical assessment. This approach should lead to alternative methods for measuring self-diffusion coefficients.     

Association between ammonium monovanadate and β-cyclodextrin as seen by NMR and transport techniques

The interaction between vanadium (V) and the carbohydrate β-cyclodextrin (β-CD) has been studied in aqueous solutions (pH ≈ 7.5, 298.15 K) using multinuclear NMR spectroscopy, coupled with measurements of diffusion coefficients and electrical conductivity. The transport properties of vanadate ion solutions are markedly influenced by the presence of β-CD. Data from ⁵¹V, ¹H and ¹³C NMR spectroscopy show that these effects are due to strong interactions between this carbohydrate and vanadate due to formation of 2:1 (β-CD:vanadate) complexes. The formation of such 2:1 complexes is also supported by molecular mechanics calculations. Complexation is seen by conductometric and diffusion techniques to lead to a significant decrease in the molar conductivity and diffusion coefficient of vanadate solutions in the presence of β-CD. Using the above stoichiometry, it has been possible to calculate the association constant, leading to the value K = 4.3 × 10⁴ M⁻² from the analysis of the conductivity data.     

Proton conducting ionic liquid organization as probed by NMR: self-diffusion coefficients and heteronuclear correlations

The structure and local organization of new proton conducting ionic liquids (PCILs) obtained by reacting alkylamine with various acids were deciphered by complementary 1- and 2-D heteronuclear NMR experiments. One the one hand, PFG NMR yielded the self-diffusion coefficients of the PCIL components (and thus information on their possible concerted translational motions), while on the other hand, 13C, 1H, and 15N, 1H correlation and intermolecular Overhauser experiments gave insight into the nature of protonic species and ion-pairing behavior.     

Characterization of fractionated asphaltenes by UV-vis and NMR self-diffusion spectroscopy

Asphaltenes have been fractionated by liquid/liquid extraction, yielding four subfractions. The characteristics of fractionated asphaltenes were studied with respect to solubility, aromaticity, heteroatom content, and diffusion behavior. It was observed that asphaltenes from the four subfractions showed variations in their tendency to flocculate and also distinct differences in aromaticity. Furthermore, NMR self-diffusion studies showed that the average diffusion coefficients varied for asphaltenes from the different subfractions. The results suggest a variation in average size and stability between asphaltenes, depending on what subfraction they belong to. The subfraction that consisted of asphaltenes with the largest average size and the highest aromaticity was also found to contain the asphaltenes that had the strongest tendency to flocculate.     

A unidirectional energy transfer cascade process in a ruthenium junction self-assembled by alpha- and beta-cyclodextrins

A Ru(II) complex, Ru(alpha2beta), with a trisbipyridyl core and two different receptor sites, alpha- and beta-cyclodextrins, acts as a junction to recognize photoactive guests based on anthracene, Anth, and Os(II), Os-ada, in aqueous solution. Upon light excitation of the self-assembled system Anth.Ru(alpha2beta).Os-ada, an energy cascade process takes place from the Anth guest to the Ru(alpha2beta) core, and subsequently, the energy is funneled to the Os-ada guest. The rates of the two photoinduced processes are determined by time-resolved emission and transient absorption spectroscopic techniques. The system introduces a directed self-assembly approach to unidirectional wires that can lead to nanosized arrays by judicious selection of the individual components.     

The association of urethane-polyethyleneoxide (HEUR) thickeners,as studied by NMR self-diffusion measurements

The concentration and molecular weight dependence of the self-diffusion coefficient (D _self) of associative polymers of HEUR-type in aqueous solution have been investigated using FT-PGSE-NMR technique. The idea of three-dimensional network formation as a result of aggregation of the hydrophobic end-groups of the polymer in junctions is supported through the observed dramatic lowering ofD _self with increased concentration. The network-formation efficiency depends on the polymer molecular weight as well as the hydrophobicity of the end-groups.A double logarithmic dependence of the self-diffusion coefficient versus concentration (c) has been observed:D _selfc ^–a1,a2 . The first exponent,a ₁, is valid at low concentration, <1% polymer per weight solution, and ranges from 0.5 to 1, whereas the second exponent,a ₂, describing systems of higher concentration, ranges from 2 to 2.7.     

Chemical clockwise tridifferentiation of alpha- and beta-cyclodextrins: bascule-bridge or deoxy-sugars strategies

The selective and efficient functionalisation of large concave molecules is a chemical challenge opening the door to various applications, such as artificial enzymes. We propose here a method, based on deprotection of benzylated cyclodextrins, to selectively access a variety of complex structures with two or three new different functionalities on the primary platform. Our strategy is based on a mechanistic hypothesis involving the approach of an aluminium reagent between the primary oxygen atom and the endocyclic one of the same sugar unit. Due to its cyclic directionality, a change in steric hindrance on a given position of the cyclodextrin has a different effect on the clockwise or the counterclockwise directions. This concept is illustrated and exploited in two complementary ways: deoxygenation of the primary position of two diametrically opposed sugars induces a debenzylation reaction on the neighbouring clockwise sugars of alpha- and beta-cyclodextrins. Reversible capping, or bascule-bridging, of the same pair of sugars has the same effect on the debenzylation of alpha-cyclodextrin, but induces an important change of the geometry of beta-cyclodextrin, hence allowing the selective access to yet another functionalisation pattern. A combined use of deoxygenation and bascule-bridging allows the access to an alpha-cyclodextrin with its three pairs of primary functions differentiated and ready for further modifications. Bascule-bridge or deoxy-sugars are two complementary means to operate steric decompression and induce selective reactions to efficiently access a number of new patterns of functionalities on concave molecules.     

NMR研究草酸双过氧钒配合物与精氨酸的相互作用

应用多核(^1H,^13c,^15N和^51V)NMR、二维扩散排序谱(2D DOSY)、变温NMR以及电喷雾质谱(ESI-MS)等谱学方法研究草酸双过氧钒配合物与精氨酸(Arg)的相互作用,发现该相互作用体系可生成以氨基配位的新过氧钒物种[OV(O2)2Arg]^-,研究结果表明综合利用上述谱学方法有助于揭示此类相互作用体系的反应过程和配位机制。     

Use of styrene radical cations as probes for the complexation dynamics of charged guests with alpha- and beta-cyclodextrins

The complexation dynamics of radical cations with cyclodextrins (CD) was studied using photophysical techniques. Radical cations of 4-vinylanisole and trans-anethole were formed within alpha- and beta-CD cavities by two-photon photolysis of the respective styrene precursors. Exit of the radical cations from alpha-CD complexes with 1: 1 and 1:2 (guest: CD) stoichiometries and beta-CD complexes with 1:1 stoichiometries occurred with lifetimes shorter than 100 ns. Most of the radical cations formed escape from the CD cavities, but a small portion do react with alpha-CD when this host is present in high concentrations.     

Studies on the Interactions between Potassium oxalato-oxodiperoxovanadate and Histidine by NMR and MS

K3[VO(O2)2(C2O4)]2H2O, (abbr. BpV (ox)) pertains to peroxovanadium (abbr. pV) complexes, which have been attracted considerable attention nowadays, since they are inhibitors of tyrosine phosphatase and may be developed into a new kind of drugs for the treatment of diabetes1. According to the evidence on water-biperoxovanadium, the molecular mechanism of insulin-like effects of pV involves in irreversibly oxidizing the catalytic cysteine at the active site of the target enzyme2,3. However…     

NMR self-diffusion study of polyethylene and paraffin melts

The self-diffusion coefficient D of paraffin and polyethylene melts—covering the range between N = 19 and 10³ where N is the number of monomeric units—was measured by the pulsed-magnetic-field-gradient NMR method for diffusion times between 3 ms and 1 s. For the paraffins, D is proportional to N^?2 though the molecular weights are smaller than the critical molecular weight for entanglement. In polyethylene, melts a strong dependence of the diffusion coefficient on the diffusion time is observed, whereas no such dependence is found in paraffin melts. A mathematical formalism for describing spin-echo attenuation in terms of a velocity autocorrelation function is shown to yield qualitative agreement with the experimental results.     

Interactions between gemini surfactants, 12-s-12, and beta-cyclodextrin as investigated by NMR diffusometry and electric conductometry

The interaction between beta-cyclodextrin (CD) and gemini surfactant of the type alkyl-alpha,omega-bis(dodecyldimethylammonium bromide) with different spacer lengths of 2, 8, and 10 carbons has been investigated by means of electric conductivity (EC) and proton self-diffusion NMR at 298 K. The formation of a 2:1 (CD:gemini) complex in a two-step mechanism is observed with the first association constant (K(11)) higher than the second one (K(21)), but both relatively small in comparison with single C(12)-tailed surfactant. The value of the association constants increased with spacer length both for the first and second associated CD, which indicates that the available space on the gemini molecule is important. The magnitudes of the association constant both for the first and second complexation are discussed. The first association constant is small (when compared with the homologous single-chain surfactant) due to hydrophobic interaction between the hydrocarbon tails within the gemini molecule, while the second association constant shows no cooperativity and its magnitude is discussed in terms of steric constrains.     

咪唑类配体与双过氧钒配合物相互作用的NMR研究

为探讨咪唑环上取代基团对反应平衡的影响, 在模拟生理条件(0.15 mol·L-1 NaCl溶液)下, 应用多核(1H、13C和51V)、扩散排序谱(DOSY)以及变温NMR等谱学技术研究双过氧钒配合物NH4[OV(O2)2{2-(2’-Pyri-dine)-Imidazole}]·4H2O(简写为bpV(Imi-Py))和咪唑类配体(咪唑、2-甲基鄄咪唑、4-甲基-咪唑和组氨酸)的相互作用, 其从强到弱的顺序为咪唑≈4-甲基-咪唑>2-甲基-咪唑>组氨酸. 研究结果表明, 咪唑环上取代基团空间位阻对反应平衡产生较大影响,同时竞争配位的结果导致新的6 配位过氧物种[OV(O2)2L]-(L 为咪唑类配体)的生成, 当配体为4-甲基-咪唑和组氨酸时, 生成的则是一对异构体.     

Transport properties in two pyrrolidinium-based protic ionic liquids as determined by conductivity,viscosity and NMR self-diffusion measurements

Conductivity and viscosity measurements of pyrrolidinium hydrogen sulfate, [Pyrr][HSO₄], and pyrrolidinium trifluoroacetate [Pyrr][CF₃COO] were performed at various temperatures over a wide temperature range (i.e., from T = 273 K to 353 K). The results were utilized in the Stokes–Einstein equation to investigate the proton conductivity in both PILs. The self-diffusion coefficients (D) of the cation and anion species in both studied PILs were independently determined in the same temperature range by observing ¹H and ¹⁹F nuclei with the pulsed-field gradient spin-echo NMR technique. With regard to the mechanism of self-diffusion, based on the values of the coefficients, a relatively large difference was observed between the two ionic liquids (ILs). Independently of the temperature, the D values indicated that the diffusion of both ions was similar, signifying that they were tightly bound together as ion pairs. Nevertheless, mobile protons attached to nitrogen atoms exhibited D values five times higher than those of the pyrrolidinium cation or hydrogenosulfate anion in [Pyrr][HSO₄], and twofold those in the case of [Pyrr][CF₃CO₂]. In order to comment d.c. conductivities results, the self-diffusion coefficients determined by PGSE NMR were converted into charge diffusivity D by means of the Nernst–Einstein equation. In a similar way, a viscosity-related diffusivity D was calculated with the aid of the Stokes–Einstein equation. The temperature-independent cation transference number and the effective hydrodynamic radius were also deduced from these equations. Such parameters play an important role in charge and mass transports in ILs. Moreover, proton conduction follows a combination of Grotthuss- and vehicle-type mechanisms, which confirms that Brønsted acid–base ionic liquid systems are good candidates as proton conductors in fuel cells or supercapacitor electrolyte devices operating under anhydrous conditions at elevated temperatures.     

双过氧钒配合物与吡啶类配体相互作用的NMR研究

为探讨单齿/双齿吡啶类配体对反应平衡的影响,在模拟生理条件下(0.15mol·L-1NaCl溶液),应用多核(1H、13C和51V)多维(COSY,HSQC和HMBC)以及变温NMR技术研究双过氧钒配合物[OV(O2)2(D2O)]-/[OV(O2)2(HOD)]-(简写为bpV)与系列吡啶类配体的相互作用,研究结果表明bpV与有机配体的反应性从强到弱的顺序为:2,2′-联吡啶2,2′-联吡啶-4,4′-二甲酸根吡啶异烟酸根,这说明双齿吡啶类配体配位能力强于单齿配体,而不带羧基的吡啶类配体(单齿或双齿)配位能力强于所对应的带羧基的取代吡啶,竞争配位导致一系列新的6配位(配体为吡啶或异烟酸根)或7配位(配体为2,2′-联吡啶或2,2′-联吡啶-4,4′-二甲酸根)的过氧钒物种[OV(O2)2LL′]n-(LL′=吡啶类配体,n=1,2,3)生成。     

NMR研究N-甲基咪唑与双过氧钒配合物的相互作用

为探讨过氧钒配合物上有机配体对反应平衡的影响, 在模拟生理条件下(0.15 mol/L NaCl溶液), 应用多核(¹H, ¹³C和⁵¹V)多维(COSY) NMR以及变温技术等谱学方法研究双过氧钒配合物[OV(O₂)₂LL']ⁿ− [n＝1～3, LL'＝oxalate (缩写为oxa)、picolinate(缩写为pic)、bipyridine(缩写为bipy)和1,10-phenanthroline(缩写为phen), 与它们配位的含钒物种分别缩写为bpV(oxa), bpV(pic), bpV(bipy)和bpV(phen)]与N-甲基咪唑(缩写为N-Me-Im)的相互作用, 实验结果表明N-Me-Im与4种双过氧钒配合物的反应活性从强到弱的顺序为: bpV(oxa)＞bpV(pic)＞bpV(bipy)＞bpV(phen). 研究表明金属中心上配体的配位能力和空间位阻都对反应平衡产生较大的影响, 同时竞争配位的结果导致新的过氧物种[OV(O₂)₂(N-Me-Im)]⁻的生成, 而利用上述谱学方法则有助于揭示此类相互作用体系的反应过程和配位方式.     

The inclusion of the drug diflunisal by alpha- and beta-cyclodextrins. A nuclear magnetic resonance and ultraviolet spectroscopic study

¹⁹F nmr and ultraviolet spectroscopic studies show that the inclusion of the anion of the drug diflunisal (DF) by alpha- and beta- cyclodextrins (CD and CD) in water produces the complexes: DF.CD, DF.CD and DF.(CD)₂ characterized by stability constants of 17, 1.81×10⁵ and 3.07×10³ dm³mol^–1 respectively.