Refreshing the Legacy of Rudolf Nietzki: Benzene-1,2,4,5-tetramine and Related Compounds.

Like hydroquinones and quinones, aromatic compounds with multiple NH2 groups and the corresponding quinonediimines have the potential to serve as components of useful redox-active organic materials. Benzene-1,2,4,5-tetramine (BTA) and its oxidized form BTA-H2 offer a promising redox pair of this type, and the compounds have proven to be useful in many areas of chemistry. However, key aspects of their behavior have remained poorly studied, such as the nature of their protonated forms, their preferred molecular structures, their reactivity, and their organization in condensed phases. In the present work, we have used a combination of improved methods of synthesis, computation, spectroscopic studies, and structural analyses to develop a deeper understanding of BTA, BTA-H2, their salts, and related compounds. The new knowledge is expected to accelerate exploitation of the compounds in areas of materials science where desirable properties can only be attained by properly controlling the organization of molecular components.

Diphenoquinhydrones and Related Hydrogen-Bonded Charge-Transfer Complexes.

Benzoquinone and hydroquinone cocrystallize to form quinhydrone, a 1:1 complex with a characteristic structure in which the components are positioned by hydrogen bonds and charge-transfer interactions. We have found that analogous diphenoquinhydrones can be made by combining 4,4'-diphenoquinones with the corresponding 4,4'-dihydroxybiphenyls. In addition, mixed diphenoquinhydrones can be assembled from components with different substituents, and mismatched quinhydrones can be made from benzoquinones and dihydroxybiphenyls. In all cases, the components of the resulting structures are linked in alternation by O-H···O hydrogen bonds to form essentially planar chains, which stack to produce layers in which π-donors and π-acceptors are aligned by charge-transfer interactions. Geometric parameters, computational studies, and spectroscopic properties of diphenoquinhydrones show that the key intermolecular interactions are stronger than those in simple quinhydrone analogues. These findings demonstrate that the principles of modular construction underlying the formation of classical quinhydrones can be generalized to produce a broad range of hydrogen-bonded charge-transfer materials in which the components are positioned by design.

Using Nuclear Magnetic Resonance Spectroscopy to Probe Hydrogels Formed by Sodium Deoxycholate.

Hydrogels of bile acids and their salts are promising materials for drug delivery, cellular immobilization, and other applications. However, these hydrogels are poorly understood at the molecular level, and further study is needed to allow improved materials to be created by design. We have used NMR spectroscopy to probe hydrogels formed from mixtures of formic acid and sodium deoxycholate (NaDC), a common bile acid salt. By assaying the ratio of deoxycholate molecules that are immobilized as part of the fibrillar network of the hydrogels and those that can diffuse, we have found that 65% remain free under typical conditions. The network appears to be composed of both the acid and salt forms of deoxycholate, possibly because a degree of charge inhibits excessive aggregation and precipitation of the fibrils. Spin-spin relaxation times provided a molecular-level estimate of the temperature of gel-sol transition (42 °C), which is virtually the same as the value determined by analyzing macroscopic parameters. Saturation transfer difference (STD) NMR spectroscopy established that formic acid, which is present mainly as formate, is not immobilized as part of the gelating network. In contrast, HDO interacts with the network, which presumably has a surface with exposed hydrophilic groups that form hydrogen bonds with water. Moreover, the STD NMR experiments revealed that the network is a dynamic entity, with molecules of deoxycholate associating and dissociating reversibly. This exchange appears to occur preferentially by contact of the hydrophobic edges or faces of free molecules of deoxycholate with those of molecules immobilized as components of the network. In addition, DOSY experiments revealed that gelation has little effect on the diffusion of free NaDC and HDO.

Use of Solid-State NMR Spectroscopy for the Characterization of Molecular Structure and Dynamics in Solid Polymer and Hybrid Electrolytes.

Solid-state NMR spectroscopy is an established experimental technique which is used for the characterization of structural and dynamic properties of materials in their native state. Many types of solid-state NMR experiments have been used to characterize both lithium-based and sodium-based solid polymer and polymer-ceramic hybrid electrolyte materials. This review describes several solid-state NMR experiments that are commonly employed in the analysis of these systems: pulse field gradient NMR, electrophoretic NMR, variable temperature T1 relaxation, T2 relaxation and linewidth analysis, exchange spectroscopy, cross polarization, Rotational Echo Double Resonance, and isotope enrichment. In this review, each technique is introduced with a short description of the pulse sequence, and examples of experiments that have been performed in real solid-state polymer and/or hybrid electrolyte systems are provided. The results and conclusions of these experiments are discussed to inform readers of the strengths and weaknesses of each technique when applied to polymer and hybrid electrolyte systems. It is anticipated that this review may be used to aid in the selection of solid-state NMR experiments for the analysis of these systems.

A Molecular Necklace: Threading ß-Cyclodextrins onto Polymers Derived from Bile Acids.

A molecular necklace of polypseudorotaxanes was prepared by threading ß-cyclodextrins (ß-CD) onto biodegradable and thermoresponsive polyurethanes derived from bile acids. These polyurethanes were synthesized via a simple step condensation of bile acid-based dicarbonate with poly(ethylene glycol)-diamine. The ß-CD rings slide onto the poly(ethylene glycol) segments and selectively recognize the bile acid units of the polyurethane chains, whereas the poly(ethylene glycol) segments remain crystalline with a lower crystallinity. This bio-compound-derived molecular necklace can be visualized by scanning tunneling microscopy. The polypseudorotaxanes show thermosensitivity in water and the phase transition temperature may be fine-tuned by varying the molar ratios of ß-CD to the bile acid units. Such an interesting necklace model of polypseudorotaxane constructed from natural compounds may lead to the further exploration of their applications, such as as an enzyme model, due to their biological nature.

Coordination-driven self-assembly of polyoxometalates into discrete supramolecular triangles.

Pd(II)-directed self-assembly of a 3-pyridyl grafted Lindqvist hexavanadate led to the formation of a unique trimeric species, as confirmed by a variety of techniques, including pulsed-field gradient NMR spectroscopy and high-resolution ESI mass spectrometry.

NMR imaging of high-amylose starch tablets. 2. Effect of tablet size.

Carbohydrate polymers are widely used for pharmaceutical applications such as the controlled release of drugs. The swelling and water mobility in high-amylose starch tablets are important parameters to be determined for these applications. They have been studied at different time intervals by nuclear magnetic resonance imaging (NMRI) after the immersion of the samples in water. These tablets have a hydrophilic matrix, which swells anisotropically and forms a hydrogel in water. NMRI shows clearly the anisotropy of the water penetration and the swelling along the radial and axial dimensions of the tablets. Empirical relationships are established to describe the kinetics of water penetration and swelling of the tablets. Results show that water uptake and tablet swelling strongly depend on the size of the tablets. Gravimetric measurements of water uptake were also performed in comparison with the NMRI results.

NMR imaging of high-amylose starch tablets. 1. Swelling and water uptake.

Pharmaceutical tablets made of modified high-amylose starch have a hydrophilic polymer matrix into which water can penetrate with time to form a hydrogel. Nuclear magnetic resonance imaging was used to study the water penetration and the swelling of the matrix of these tablets. The tablets immersed in water were imaged at different time intervals on a 300 MHz NMR spectrometer. Radial images show clearly the swelling of the tablets and the water concentration profile. The rate constants for water diffusion and the tablet swelling were extracted from the experimental data. The water diffusion process was found to follow case II kinetics at 25 degrees C. NMR imaging also provided spin density profiles of the water penetrating inside the tablets.