Thermally Induced Protonation of Conducting Polyaniline Film by Dibutyl Phosphite Conversion to Phosphate.

The blue thin polyaniline base film changes its color to green after immersion of the film into dibutyl phosphonate. The green color of the film converts to a greenish-blue after heating to 200 °C in air, which is characteristic for the protonated conducting form of polyaniline. This is in contrast to the "standard" polyaniline hydrochloride, which is transformed into a cross-linked polyaniline base under such conditions. To explain this unexpected observation, the interaction of polyaniline base with dibutyl phosphonate at ambient conditions and after heating to 200 °C was studied using UV-visible, FTIR and Raman spectroscopies. On the basis of these studies, we propose that the dibutyl phosphite tautomeric form of dibutyl phosphonate, which interacts with polyaniline base at 20 °C, converts to the oxidized form, dibutyl phosphate, at 200 °C and subsequently protonates the film. Quantum-chemical modeling of the interaction of polyaniline base with dibutyl phosphite and dibutyl phosphate supports this explanation.

Poly(N-isopropylacrylamide)-clay based hydrogels controlled by the initiating conditions: evolution of structure and gel formation.

The formation of the hydrogel poly(N-isopropylacrylamide)-clay (LAPONITE®) by redox polymerization was investigated, and the main factors governing the gel build-up were determined. The significant effect of the redox initiating system ammonium peroxodisulfate (APS) and tetramethylethylenediamine (TEMED) on gel formation and structure was established, making it possible to control the structure of the gel. Moreover, the pre-reaction stage involving the quality of the clay exfoliation in an aqueous suspension and the interaction of reaction components with the clay play a role in controlling the polymerization and gel structure. The molecular and phase structure evolution during polymerization was followed in situ by the following independent techniques: Fourier transform infrared spectroscopy (FTIR), chemorheology, small-angle X-ray scattering (SAXS) and ultraviolet-visible spectroscopy (UV/Vis). The combination of these methods enabled us to describe in detail particular progress stages during the gel formation and determine the correlation of the corresponding processes on a time and conversion scale. The mechanism of gel formation was refined based on these experimental results.

The effect of micellization-induced deprotonation on the associative behavior of a carboxyl modified Pluronic P85.

Thermoresponsive polymeric surfactant CAE85 is a telechelic carboxyl group derivative of Pluronic P85 and its carboxyl end-groups undergo deprotonation into carboxylate groups upon micellization. Micelle formation and disintegration were studied here by means of small angle X-ray scattering, FTIR and Raman spectroscopy, quantum mechanical calculations and dynamical mechanical analysis. The deprotonation was observed in aqueous solutions of CAE85 for concentrations from 5 wt% to 30 wt% at temperatures above the corresponding critical micellization temperature (CMT). The most likely cause is a difference between the proton dissociation constant of the micelle (pK(m)) and the proton dissociation constant of the unimers in solution (pK(a)); our observations indicate that pKm < pK(a). For concentrations up to 15 wt%, the presence of carboxylate groups in CAE85 lowered the CMT in comparison with P85. In addition, the behavior of CAE85 was generally not thermo-reversible and reproducible upon cooling. Quantum chemical calculations showed that, in the dense micelle corona, the deprotonated states were more stable than hydrogen-bonded states of neutral molecules, which is likely to affect the equilibrium processes in the micelle. In contrast to the unmodified P85, no gelation was observed in the case of CAE85. By studying the processes at all the levels of organization from nanoscale charge formation through micellization to the macroscale process of gelation, our understanding of polymeric micelle formation may be advanced.

Quantification of structural changes of UHMWPE components in total joint replacements.

BACKGROUND: At present time the number of implantations of joint replacements as well as their revisions increases. Higher demands are required on the quality and longevity of implants. The aim of this work was to determine the degree of oxidative degradation and the amount of free/residual radicals in selected ultra-high molecular weight polyethylene (UHMWPE) components of the joint replacements and demonstrate that the measured values are closely connected with quality and lifetime of the polymer components. METHODS: We tested both new (4 samples) and explanted (4 samples) UHMWPE polymers for total joint replacements. The samples were characterized by infrared spectroscopy (IR), electron spin resonance (ESR) and microhardness (MH) test. The IR measurements yielded the values of oxidation index and trans-vinylene index. The ESR measurements gave the free radicals concentration. RESULTS: In the group of new polyethylene components, we found oxidation index values ranging from 0.00-0.03 to 0.24. The trans-vinylene index values ranged from 0.044 to 0.080. The value of free radical concentration was zero in virgin and also in sample of Beznoska Company and non-zero in the other samples. In the group of explanted components, the measured values were associated with their history, micromechanical properties and performance in vivo. CONCLUSIONS: We demonstrated that measuring of oxidative damage may help the orthopaedic surgeon in estimating the quality of UHMWPE replacement component and thus radically to avoid early joint replacement failure due to worse polyethylene quality.

Premicellar interaction of PEO-PPO-PEO triblock copolymers with partially hydrophobic alcohols: NMR study.

The interactions of three alcohols, namely, 2-butanol (BuOH), 3-methyl-2-butanol (MeBuOH), and 3,3-dimethyl-2-butanol (Me2BuOH) with propylene oxide octamer (PO8) and the copolymers (EO)8(PO)13(EO)8(L35) and (EO)13(PO)30(EO)13(L64) in D2O were studied using (13)C NMR spectra and relaxations and (1)H PFG NMR diffusion measurements. For L64, it was shown that the temperature at which the PO chain starts to change its conformation under dehydration decreases by 6 K for each additional methyl group in the alcohol molecule (i.e. with increasing its hydrophobicity), and the analogous conformation states are attained at temperatures approximately 10 K lower compared using ketonic analogs of the alcohols under the same conditions. Also, the first signs of L64 aggregation, according to the normalized diffusion coefficients, are at temperatures 7, 10, and 13 K lower for BuOH, MeBuOH, and Me2BuOH, respectively. These effects are much weaker for (PO)13 in L35 or nonexistent for (PO)8 in PO8, thus showing the role of cooperativity in dehydration and aggregation processes. According to diffusion measurements, the molar fraction of the alcohol hydrogen bonded to L64 increases with its hydrophobicity and, in an apparent conflict with thermodynamics, with increasing temperature at which also higher NOE can be observed. Strong hydrogen bond interaction, which is in cooperation with hydrophobic interaction, does not preclude the exchange between bound and free states of the alcohol, however. Using (13)C transverse relaxation, its correlation time is shown to be of the order of 10 ms.

Effect of Polydopamine Coating of Cellulose Nanocrystals on Performance of PCL/PLA Bio-Nanocomposites.

In bio-nanocomposites with a poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) matrix with neat and polydopamine (PDA)-coated cellulose nanocrystals (CNCd), the use of different mixing protocols with masterbatches prepared by solution casting led to marked variation of localization, as well as reinforcing and structure-directing effects, of cellulose nanocrystals (CNC). The most balanced mechanical properties were found with an 80/20 PLA/PCL ratio, and complex PCL/CNC structures were formed. In the nanocomposites with a bicontinuous structure (60/40 and 40/60 PLA/PCL ratios), pre-blending the CNC and CNCd/PLA caused a marked increase in the continuity of mechanically stronger PLA and an improvement in related parameters of the system. On the other hand, improved continuity of the PCL phase when using a PCL masterbatch may lead to the reduction in or elimination of reinforcing effects. The PDA coating of CNC significantly changed its behavior. In particular, a higher affinity to PCL and ordering of PLA led to dissimilar structures and interface transformations, while also having antagonistic effects on mechanical properties. The negligible differences in bulk crystallinity indicate that alteration of mechanical properties may have originated from differences in crystallinity at the interface, also influenced by presence of CNC in this area. The complex effect of CNC on bio-nanocomposites, including the potential of PDA coating to increase thermal stability, is worthy of further study.

The Effects of the Deacetylation of Chitin Nanowhiskers on the Performance of PCL/PLA Bio-Nanocomposites.

The multiple roles of organic nanofillers in biodegradable nanocomposites (NC) with a blend-based matrix is not yet fully understood. This work highlights combination of reinforcing and structure-directing effects of chitin nanowhiskers (CNW) with different degrees of deacetylation (DA), i.e., content of primary or secondary amines on their surface, in the nanocomposite with the PCL/PLA 1:1 matrix. Of importance is the fact that aminolysis with CNW leading to chain scission of both polyesters, especially of PLA, is practically independent of DA. DA also does not influence thermal stability. At the same time, the more marked chain scission/CNW grafting for PLA in comparison to PCL, causing changes in rheological parameters of components and related structural alterations, has crucial effects on mechanical properties in systems with a bicontinuous structure. Favourable combinations of multiple effects of CNW leads to enhanced mechanical performance at low 1% content only, whereas negative effects of structural changes, particularly of changed continuity, may eliminate the reinforcing effects of CNW at higher contents. The explanation of both synergistic and antagonistic effects of structures formed is based on the correspondence of experimental results with respective basic model calculations.

European Database of Explanted UHMWPE Liners from Total Joint Replacements: Correlations among Polymer Modifications, Structure, Oxidation, Mechanical Properties and Lifetime In Vivo.

This contribution lays the foundation for the European database of explanted UHMWPE liners from total joint replacements. Three EU countries (Czech Republic, Italy and Spain) have joined their datasets containing anonymized patient data (such as age and BMI), manufacturer data (such as information on UHMWPE crosslinking, thermal treatment and sterilization), orthopedic evaluation (such as total duration of the implant in vivo and reasons for its revision) and material characterization (such as oxidative degradation and micromechanical properties). The joined database contains more than 500 entries, exhibiting gradual growth, and it is beginning to show interesting trends, which are discussed in our contribution, including (i) strong correlations between UHMWPE oxidative degradation, degree of crystallinity and microhardness; (ii) statistically significant differences between UHMWPE liners with different types of sterilization; (iii) realistic correlations between the extent of oxidative degradation and the observed reasons for total joint replacement failures. Our final objective and task for the future is to continuously expand the database, involving researchers from other European countries, in order to create a robust tool that will contribute to the better understanding of structure-properties-performance relationships in the field of arthroplasty implants.

Interaction of hydrated protons with octyl-phenyl-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO): NMR and theoretical study.

Interaction of octyl-phenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO, the 'classical' rare metal extraction agent) with fully ionized hydrated protons (HP) was studied in acetonitrile-d(3) using (1)H, (13)C, (31)P NMR, PFG NMR and magnetic relaxation. The experimental results were confronted with high-precision ab initio DFT calculations. Relative chemical shifts of NMR signals of CMPO (0.01 mol/L) under the presence of HP in the molar ratio ß = 0-2.0 mol/mol show binding between CMPO and HP. Self-diffusion measurements using (1)H PFG NMR demonstrate that larger complexes with higher content of CMPO are generally formed at ß < 0.75. Analyzing the collective dependence of (13)C and (31)P NMR chemical shifts on ß by the use of program LETAGROP, we obtained very good fitting for the assumed coexistence of two complexes (CMPO)(2)·HP (C(2)) and CMPO.HP (C(1)). The logarithms of the respective stabilization constants log K(i) were found to be 7.518 (C(2)) and 4.581 (C(1)). The system dynamics was studied by measuring the transverse (1)H NMR relaxation using CPMG sequence with varying delays t(p) between the π pulses in the mixtures with ß = 0.4-0.8. The following exchange correlation times were obtained: τ(10) = 2.35 × 10(-5), τ(20) = 0.82 × 10(-4), τ(21) = 0.45 × 10(-3) s. The DFT calculations support the conclusion that the complexes C(1) and C(2) are the main species in the mixtures of CMPO with HP. They also agree with the NMR and FTIR observation that the main site to which H(3) O(+) is bound is the P=O group, whereas the amide group does not form a strong bond with the ion when excess water molecules are present.

Enhanced Ordering of Block Copolymer Thin Films upon Addition of Magnetic Nanoparticles.

The influence of magnetite nanoparticles coated with poly(acrylic acid) (Fe3O4@PAA NPs) on the organization of block copolymer thin films via a self-assembly process was investigated. Polystyrene-b-poly(4-vinylpyridine) films were obtained by the dip-coating method and thoroughly examined by X-ray reflectivity, transmission electron microscopy, atomic force microscopy, and grazing incidence small-angle scattering. Magnetic properties of the films were probed via superconducting quantum interference device (SQUID) magnetometry. It was demonstrated that due to the hydrogen bonding between P4VP and PAA, the Fe3O4@PAA NPs segregate selectively inside P4VP domains, enhancing the microphase separation process. This in turn, together with employing carefully optimized dip-coating parameters, results in the formation of hybrid thin films with highly ordered nanostructures. The addition of Fe3O4@PAA nanoparticles does not change the average interdomain spacing in the film lateral nanostructure. Moreover, it was shown that the nanoparticles can easily be removed to obtain well-ordered nanoporous templates.

Synergistic effects in Methylcellulose/Hydroxyethylcellulose blend: Influence of components ratio and graphene oxide.

A specific feature of water-soluble polysaccharides is formation of organized structures in solutions. This study deals with an unexpected effect of 2-hydroxyethylcellulose (HEC) on structure and mechanical performance of methylcellulose (MC) films. The values of modulus with 5 and 10 % HEC content exceed those of the linear model, which indicates synergistic effect consisting in formation of ordered structures. However, higher content of HEC leads to worse properties corresponding to contribution of its lower parameters. The structural transformations are confirmed by XRD and polarized-light microscopy. Ability of HEC to support formation of ordered structures in MC solutions is indicated by rheology. Important fact is that low graphene oxide (GO) content has a high reinforcing effect on neat MC or HEC, but its presence in blends is accompanied by elimination of HEC-induced structural transformations. The results confirm complex effect of blending and GO on structure and properties of the MC/HEC system.

Nano-modified epoxy: the effect of GO-based complex structures on mechanical performance.

The application of nanofillers (NFs) in multicomponent polymer systems is accompanied by important structure-directing effects that are more marked in partially miscible systems, such as polymer-modified epoxy. This study deals with rubber-modified epoxy using different combinations of GO and amine-terminated butadiene-acrylonitrile copolymer (ATBN), including in situ and pre-made grafting. Moreover, GO grafted via planar epoxy groups or solely edge-localized carboxyls was used. It is shown that the grafted ATBN chains promote the assembly of GO-g-ATBN into nacre-mimicking lamellar structures instead of usual exfoliation in thermoplastics. This complex structure of elastically embedded GO leads to the best mechanical performance. It is obvious that a small concentration of the grafted polymer exceeds the contribution of a higher concentration of separately added ATBN. The results highlight the important effect of the degree of grafted chains and geometry of the internal structure of the self-assembled arrays and their effect on the mechanical performance.

Capillary electrophoretic and computational study of the complexation of valinomycin with rubidium cation.

This study is focused on the characterization of interactions of valinomycin (Val), a macrocyclic dodecadepsipeptide antibiotic ionophore, with rubidium cation, Rb(+). Capillary affinity electrophoresis was employed for the experimental evaluation of the strength of the Val-Rb(+) complex. The study involved the measurement of the change of effective electrophoretic mobility of Val at increasing concentration of Rb(+) cation in the BGE. From the dependence of Val effective electrophoretic mobility on the Rb(+) cation concentration in the BGE (methanolic solution of 100 mM Tris, 50 mM acetic acid, 0-1 mM RbCl), the apparent binding (stability) constant (K(b)) of the Val-Rb(+) complex in methanol was evaluated as log K(b)=4.63+/-0.27. According to the quantum mechanical density functional theory calculations employed to predict the most probable structure of Val-Rb(+) complex, Val is stabilized by strong non-covalent bond interactions of Rb(+) with six ester carbonyl oxygen atoms so that the position of the "central" Rb(+) cation in the Val cage is symmetric.

Hydration modes of an amphiphilic molecule: NMR, FTIR, and theoretical study of the interactions in the water-lutidine system.

Using (1)H and (13)C NMR spectra and relaxations, PFG NMR diffusion measurements, FTIR spectra, and quantum-chemical structure predictions and optimizations on the MP2/6-31G(d) level, we have studied interactions between water (W) and lutidine (2,6-dimethylpyridine, L) in a wide range of ratios. At low W content up to 35%, W was found to bind to L by an O-H***N hydrogen bond and form transient L-W aggregates containing two to four L molecules in cooperation with two to three other W molecules. At higher W content, these aggregates are gradually cleaved to single L molecules enwrapped by a hydration shell anchored in an O-H***N hydrogen bond. At all compositions of the mixture, the various hydrate forms are in fast mutual exchange with a correlation time on the order of 1 x 10(-5) s.

Interaction of hydrated protons with trioctylphosphine oxide: NMR and theoretical study.

Interaction of trioctylphosphine oxide (TOPO) with fully ionized hydrated protons (HP) was studied in acetonitrile-d(3) and nitrobenzene-d(5) using (1)H, (13)C, and (31)P NMR, PFG NMR, and magnetic relaxation, and the experimental results were confronted with high-precision ab initio DFT calculations. Relative chemical shifts of NMR signals of TOPO (0.02 mol/L) under the presence of HP in the molar ratio beta = 0-2.0 mol/mol show binding between TOPO and HP. Self-diffusion measurements using (1)H PFG NMR demonstrate that larger complexes with higher content of TOPO are generally formed at beta < 0.75. Analyzing the dependence of (31)P NMR chemical shifts on beta by the use of program LETAGROP, we obtained very good fitting for the assumed coexistence of three complexes (TOPO)(i).HP (named C(i)), where i = 1, 2, 3. The logarithms of the respective stabilization constants log K(i) were found to be 3.63, 4.67, and 7.23 in acetonitrile and 3.91, 6.04, and 7.92 in nitrobenzene. The (31)P NMR chemical shifts Deltadelta(i) corresponding to these complexes are 39.35, 29.51, and 19.72 ppm in acetonitrile and 38.37, 28.47, and 18.63 ppm in nitrobenzene. These values and the calculated values of alpha(i) =[C(i)]/[TOPO](0) were utilized in the analysis of the system dynamics. This was done by measuring the transverse (31)P NMR relaxation by the CPMG sequence with varying delays t(p) between the pi pulses in the mixtures with beta = 0.5, 1.25, and 1.5. Calculating the probabilities of imaginable exchange processes shows that only three of them can have significant influence on relaxation rate R(2), namely C(1) <--> TOPO, C(2) <--> C(1), and C(3) <--> C(2). Using the slopes of the R(2)-t(p)(-1) dependences in the above three mixtures, the following correlation times were obtained: tau(10) = 2.5 x 10(-6), tau(21) = 7.4 x 10(-5), tau(32) = 11.3 x 10(-5) s. The DFT calculations support the hypothesis that complexes C(1) to C(3) are the main species in the mixtures of TOPO with HP, with the only exception that additional water molecules are bound to the complexes in the case of C(1) and C(2). Schematically, the compositions of the three stable complexes is [3TOPO.H(3)O](+), [2TOPO.H(3)O.H(2)O](+), and [TOPO.H(3)O.2H(2)O](+). The relative (31)P NMR shifts calculated for the optimized structures of C(1), C(2), and C(3) are in very good agreement with the experimentally observed values.

Capillary affinity electrophoresis and ab initio calculation studies of valinomycin complexation with Na+ ion.

In a combined experimental and theoretical approach, the interactions of valinomycin (Val), macrocyclic depsipeptide antibiotic ionophore, with sodium cation Na(+ )have been investigated. The strength of the Val-Na(+ )complex was evaluated experimentally by means of capillary affinity electrophoresis. From the dependence of valinomycin effective electrophoretic mobility on the sodium ion concentration in the BGE (methanolic solution of 20 mM chloroacetic acid, 10 mM Tris, 0-40 mM NaCl), the apparent binding (stability) constant (K(b)) of the Val-Na(+ )complex in methanol was evaluated as log K(b) = 1.71 +/- 0.16. Besides, using quantum mechanical density functional theory (DFT) calculations, the most probable structures of the nonhydrated Val-Na(+) as well as hydrated Val-Na(+).H(2)O complex species were proposed. Compared to Val-Na(+), the optimized structure of Val-Na(+).H(2)O complex appears to be more realistic as follows from the substantially higher binding energy (118.4 kcal/mol) of the hydrated complex than that of the nonhydrated complex (102.8 kcal/mol). In the hydrated complex, the central Na(+) cation is bound by strong bonds to one oxygen atom of the respective water molecule and to four oxygens of the corresponding C=O groups of the parent valinomycin ligand.

Control of Gelation and Properties of Reversible Diels-Alder Networks: Design of a Self-Healing Network.

Reversible Diels-Alder (DA) type networks were prepared from furan and maleimide monomers of different structure and functionality. The factors controlling the dynamic network formation and their properties were discussed. Evolution of structure during both dynamic nonequilibrium and isothermal equilibrium network formation/breaking was followed by monitoring the modulus and conversion of the monomer. The gelation, postgel growth, and properties of the thermoreversible networks from tetrafunctional furan (F4) and different bismaleimides (M2) were controlled by the structure of the maleimide monomer. The substitution of maleimides with alkyl (hexamethylene bismaleimide), aromatic (diphenyl bismaleimide), and polyether substituents affects differently the kinetics and thermodynamics of the thermoreversible DA reaction, and thereby the formation of dynamic networks. The gel-point temperature was tuned in the range Tgel = 97-122 °C in the networks of the same functionality (F4-M2) with different maleimide structure. Theory of branching processes was used to predict the structure development during formation of the dynamic networks and the reasonable agreement with the experiment was achieved. The experimentally inaccessible information on the sol fraction in the reversible network was received by applying the theory. Based on the acquired results, the proper structure of a self-healing network was designed.

Role of p-Benzoquinone in the Synthesis of a Conducting Polymer, Polyaniline.

Polyaniline (PANI) and 2,5-dianilino-p-benzoquinone both are formed by oxidation of aniline in an acidic aqueous environment. The aim of this study is to understand the impact of addition of p-benzoquinone on the structure of PANI prepared by the oxidation of aniline hydrochloride with ammonium peroxydisulfate and to elucidate the formation of low-molecular-weight byproducts. An increasing yield and size-exclusion chromatography, Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy, and nuclear magnetic resonance analyses of the products show that p-benzoquinone does not act as a terminating agent in the synthesis of PANI and the content of 2,5-dianilino-p-benzoquinone increases with the increasing molar concentration of p-benzoquinone in the reaction mixture, [BzQ]. Regarding the structure of PANI, Raman and UV-visible spectra show that the doping level and the charge delocalization both decrease with the increase of [BzQ], and the FTIR spectra of the PANI bases indicate an increased concentration of benzenoid units at higher [BzQ]. We explain these observations by an increasing concentration of structural defects in PANI chains and propose a 2,5-dianilino-p-benzoquinone-like structure of these defects present as pendant groups. The bands typical of 2,5-dianilino-p-benzoquinone-like moiety are observed even in the vibrational spectra of the sample prepared without addition of p-benzoquinone. This confirms in situ oxidation of aniline to p-benzoquinone within the course of the oxidation of aniline hydrochloride to PANI.

Interaction of hydronium ion with dibenzo-18-crown-6: NMR, IR, and theoretical study.

Interaction of dibenzo-18-crown-6 (DBC) with H 3O (+) (HP) in nitrobenzene- d 5 and dichloromethane- d 2 was studied by using (1)H and (13)C NMR spectra and relaxations, FTIR spectra, and quantum chemical DFT calculations. NMR shows that the DBC*HP complex is in a dynamic equilibrium with the reactants, the equilibrium constant K being 0.66 x 10 (3), 1.16 x 10 (4), and 1.03 x 10 (4) L x mol (-1) in CD 2Cl 2, nitrobenzene, and acetonitrile, respectively. The complex appears to have a C 2 v symmetry in NMR, but FTIR combined with DFT normal mode calculations suggest that such high symmetry is only apparent and due to exchange averaging of the structure. FTIR spectra as well as energy-optimized DFT calculations show that the most stable state of the complex in solution is that with three linear hydrogen bonds of HP with one CH 2-O-CH 2 and two Ar-O-Ar oxygen atoms. The structure is similar to that found in solid state but adopts a somewhat different conformation in solution. The dynamics of exchange between bound and free DBC was studied by NMR transverse relaxation. It was found to be too fast to give reproducible results when measured with the ordinary CPMG sequence or its variant DIFTRE removing residual static dipolar interaction, but it could be established by rotating-frame measurements with high intensity of the spin-lock field. The correlation time of exchange was found to be 5.6 x 10 (-6) and 3.8 x 10 (-6) s in dichloromethane and nitrobenzene, respectively. Such fast exchange can be explained by cooperative assistance of present water molecules.

Cooperative interaction of n-butylammonium ion with 1,3-alternate tetrapropoxycalix [4]arene: NMR and theoretical study.

The interaction of 1,3-alternate tetrapropoxycalix[4]arene (1) with n-butylammonium ion (2) in CD(2)Cl(2) was examined using (1)H, (13)C and (14)N NMR spectroscopy and DFT (density functional theory) calculations. NMR shows that 1 forms with 2 an equimolecular hydrogen-bonded complex with the equilibrium constant 5.91 x 10(3) l/mol at 296 K. The structure of the complex can be shown to be asymmetric at 203 K, with 2 interacting by hydrogen bonds with the two ethereal oxygen atoms of one half of 1 and with the pi system of the other half, but is rapidly averaged to an apparent C(4h) symmetry by chemical exchange at higher temperatures. Using two related but independent techniques based on transverse and rotating-frame proton relaxation, it is shown that only an intermolecular exchange of 2 between the bound and free states takes place, in contrast to previously studied interaction of 1 with H(3)O(+). Its correlation time is 0.169 ms. It is shown by DFT calculations that such swift exchange is not possible without a cooperative interaction of both 2 and 1 with several molecules of water present. Similarities and contrasts between the exchange processes of 2 and H(3)O(+) bound to 1 are discussed, in particular with respect to the apparent quantum tunneling of the latter inside the molecule of the complex.