Thermally stable and organosoluble binaphthylene‐based poly(urea‐ether‐imide)s: one‐pot preparation and characterization

A new family of wholly aromatic poly(urea‐ether‐imide)s ( 4a–4f ) possessing binaphthylene‐twisted rings was prepared by diphenyl azidophosphate (DPAP)‐activated one‐pot polyaddition reaction of a preformed imide heterocyclic ring‐containing dicarboxylic acid, 2,2′‐bis(4‐trimellitimidophenoxy)‐ 1,1′‐binaphthyl ( 1 ) with various kinds of aromatic diamines ( 3a–3f ). At first, with due attention to structural similarity and to compare the characterization data, a model compound 2 was synthesized by the reaction of diimide‐dicarboxylic acid 1 with two mole equivalents of aniline. In this direct method, the polymers were prepared by polyaddition reactions of the in situ‐formed diisocyanate with the aromatic diamines. Molecular weights of the poly(urea‐ether‐imide)s obtained were evaluated viscometrically, and the inherent viscosities (η_inh) measured were in the range 0.10– 0.25 dl/g. All of the polymers were characterized by FT‐IR spectroscopic method and elemental analysis. All of the resulting polymers exhibited an excellent solubility in common polar solvents such as N‐methyl‐2‐pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N‐dimethylformamide (DMF), and N,N‐dimethylacetamide (DMAc). Crystallinity of the resulted polymers was evaluated by wide‐angle X‐ray diffraction (WXRD) method, and they exhibited nearly a non‐crystalline nature as evidenced by their diffractograms. The glass transition temperatures (T_g) of the polymers determined by differential scanning calorimetry (DSC) thermograms were in the range of 274–302°C. The temperatures at 10% weight loss (T_d10%) from their thermogravimetric analysis (TGA/DTG) curves were found to be in the range of 389–414°C in nitrogen atmosphere. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and computational study of two new glycoluril clips containing benzocrown ether side walls

Two new glycoluril-derived molecular clips containing benzocrown ether side walls have been synthesized via reaction of a glycoluril scaffold with two bromomethylated benzocrown ethers. The molecular geometry of their most stable structures were investigated with density functional theory at the B3LYP level of theory using STO-3G, 6-31G, and 6-311G basis sets. Then based on the obtained computer-optimized structures, the binding properties of one clip with some 5-substituted resorcinols have been calculated.     

Self‐Healing Polyester Urethane Supramolecular Elastomers Reinforced with Cellulose Nanocrystals for Biomedical Applications

Stretchable self‐healing urethane‐based biomaterials have always been crucial for biomedical applications; however, the strength is the main constraint of utilization of these healable materials. Here, a series of novel, healable, elastomeric, supramolecular polyester urethane nanocomposites of poly(1,8‐octanediol citrate) and hexamethylene diisocyanate reinforced with cellulose nanocrystals (CNCs) are introduced. Nanocomposites with various amounts of CNCs from 10 to 50 wt% are prepared using solvent casting technique followed by the evaluation of their microstructural features, mechanical properties, healability, and biocompatibility. The synthesized nanocomposites indicate significantly higher tensile modulus (approximately 36–500‐fold) in comparison to the supramolecular polymer alone. Upon exposure to heat, the materials can reheal, but nevertheless when the amount of CNC is greater than 10 wt%, the self‐healing ability of nanocomposites is deteriorated. These materials are capable of rebonding ruptured parts and fully restoring their mechanical properties. In vitro cytotoxicity test of the nanocomposites using human dermal fibroblasts confirms their good cytocompatibility. The optimized structure, self‐healing attributes, and noncytotoxicity make these nanocomposites highly promising for tissue engineering and other biomedical applications.     

Enantioselective Organocatalytic Diels–Alder Trapping of Photochemically Generated Hydroxy‐o‐Quinodimethanes

The photoenolization/Diels–Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light‐triggered process has never before succumbed to efforts to develop an enantioselective catalytic approach. Herein, we demonstrate how asymmetric organocatalysis provides simple yet effective catalytic tools to intercept photochemically generated hydroxy‐o‐quinodimethanes with high stereoselectivity. We used a chiral organic catalyst, derived from natural cinchona alkaloids, to activate maleimides toward highly stereoselective Diels–Alder reactions. An unconventional mechanism of stereocontrol is operative, wherein the organocatalyst is actively involved in both the photochemical pathway, by leveraging the formation of the reactive photoenol, and the stereoselectivity‐defining event.     

Rapid adsorption and entrapment of benzoic acid molecules onto mesoporous silica (FSM-16)

Changes in the molecular state of benzoic acid (BA) in the presence of folded sheet mesoporous material (FSM-16), which has uniformly sized cylindrical mesopores and a large surface area, were assessed with several analyses. When BA was blended with FSM-16 for 5 min (BA content=30%), the X-ray diffraction peaks of BA crystals disappeared, suggesting an amorphous state. Fluorescence analysis of the mixture showed a new fluorescence emission peak for BA at 386 nm after mixing with FSM-16. Fluorescence lifetime analysis of the BA component in the mixture at 386 nm showed a longer lifetime in comparison with that of BA crystals. The solid-state (13)C CP/MAS and PST/MAS NMR spectra of the mixture with FSM-16 showed a significantly different spectral pattern from the mixture with nonporous glass, whose NMR spectra were identical to those of BA crystals. These results indicate that BA molecules disperse quickly into the hexagonal channels of FSM-16 by a simple blending procedure and adsorbed BA molecules had clearly different physicochemical properties to BA crystals.     

Determination of reducing ends with flow injection analysis with amperometric detection: application to enzyme-hydrolysed methyl cellulose

A novel method for detection of reducing ends of sugars is proposed, based on the use of as the oxidant in combination with amperometric detection and flow injection analysis (FIA). The method is very sensitive, giving values of <10 μM for the limit of detection for a series of mono- and oligosaccharides. Samples can be analysed every 30 s, and injection can be made fully automated, making it possible to perform on-line analysis of polysaccharide samples subjected to hydrolysis. Three methylcelluloses (MC) of different qualities were hydrolysed with three different glucanases, and the concentrations of reducing ends prior to, during and after hydrolysis were determined. Differences were observed between the results obtained using different combinations of enzymes and MCs, which revealed different selectivities of the various enzymes for the different substrates. One MC was also hydrolysed and analysed in real-time for three hours. The method proposed is superior to many of the standard methods used today, which require manual labour and have a lower sensitivity. Figure Set-up used for the instrumentation in the FIA system with automated injection. A pump delivers the reaction solution to the autosampler, where the samples are injected; the sample and solution react in a temperature-controlled random coil and the response is detected using an amperometric detection cell     

NMR and structural investigations of a nonplanar iron corrolate: modified patterns of spin delocalization and coupling in a slightly saddled chloroiron(III) corrolate radical

An undecasubstituted chloroiron corrolate, octamethyltriphenylcorrolatoiron chloride, (OMTPCorr)FeCl, has been synthesized and studied by X-ray crystallography and (1)H and (13)C NMR spectroscopy. It is found that, although the structure is slightly saddled, the average methyl out-of-plane distance is only 0.63 Angstroms, while it is much greater for the dodecasubstituted porphyrinate analogue (OMTPP)FeCl (1.19 Angstroms) (Cheng, R.-J.; Chen, P.-Y.; Gau, P.-R.; Chen, C.-C.; Peng, S.-M. J. Am. Chem. Soc. 1997, 119, 2563-2569). In addition, the distance of iron from the mean plane of the four macrocycle nitrogens is also smaller for (OMTPCorr)FeCl (0.387 Angstroms) than for (OMTPP)FeCl (0.46 Angstroms). The (1)H and (13)C NMR spectra of (OMTPCorr)FeCl, as well as the chloroiron complexes of triphenylcorrolate, (TPCorr)FeCl; 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FeCl; 7,8,12,13-tetramethyl-2,3,17,18-tetraethylcorrolate, (TMTECorr)FeCl; and the phenyliron complex of 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FePh, have been assigned, and the spin densities at the carbons that are part of the aromatic ring of the corrole macrocycle have been divided into the part due to spin delocalization by corrole --> Fe pi donation and the part due to the unpaired electron present on the corrole ring. It is found that although the spin density at the beta-pyrrole positions is fairly similar to that of (TPCorr)FeCl, the meso-phenyl-carbon shift differences delta(m) - delta(p) are opposite in sign of those of (TPCorr)FeCl. This finding suggests that the radical electron is ferromagnetically coupled to the unpaired electrons on iron, rather than antiferromagnetically coupled, as in all of the other chloroiron corrolates. The solution magnetic moment was measured for (OMTPCorr)FeCl and found to be mu(eff) = 4.7 +/- 0.5 micro(B), consistent with S = 2 and ferromagnetic coupling. From this study, two conclusions may be reached about iron corrolates: (1) the spin states of chloroiron corrolates are extremely sensitive to the out-of-plane distance of iron, and (2) pyrrole-H or -C shifts are not useful in delineating the spin state and electron configuration of (anion)iron corrolates.     

Minimalist protein design: a beta-hairpin peptide that binds ssDNA

A 28-residue beta-hairpin dimer (WKWK)2 with two Trp and two Lys residues on one face of each beta-sheet was shown to form a complex with single-stranded oligonucleotides at low micromolar concentrations. Each beta-hairpin of the dimer contains a cross-strand Trp-Trp pair in a diagonal orientation which has previously been shown to create a cleft for the intercalation of aromatic guests such as adenine (J. Am. Chem. Soc. 2003, 125, 9580). The beta-hairpin dimer binds 5-residue ssDNA sequences 5'-AAAAA-3', 5'-TTTTT-3', and 5'-CCCCC-3' in water with dissociation constants in the range of 12-30 muM. A weak energetic preference for binding to sequence 5'-AAAAA-3' was observed, which is believed to result from stronger stacking interactions between Trp and the adenine base. The interaction of 5'-AAAAA-3' with the Lys and Trp residues of the peptide was evident by NMR, and a 1:1 association was demonstrated. The recognition of an 11-residue ssDNA sequence occurred with a dissociation constant of 3 muM under near-physiological ionic strength and pH, demonstrating that the beta-hairpin dimer binds ssDNA as strongly as many naturally occurring proteins. The salt dependence of the interaction of the 11-residue oligonucleotide with the peptide dimer indicates that Trp-nucleobase stacking interactions contribute about -4 kcal/mol to recognition, which is much greater than the contribution of nonionic interactions in unstructured peptides containing Trp. Moreover, recognition of the ssDNA demonstrated reduced salt dependence relative to the corresponding duplex, resulting in selectivity for ssDNA under high salt conditions. Peptide (WKWK)2 is a relevant mimic of OB-fold (oligonucleotide/oligosaccharide-binding) proteins which bind ssDNA on the surface of a beta-sheet.     

A microfluidic device for self-synchronised production of droplets

The primary requirement for a mixing operation in droplet-based microfluidic devices is an accurate pairing of droplets of reaction fluids over an extended period of time. In this paper, a novel device for self-synchronous production of droplets has been demonstrated. The device uses a change in impedance across a pair of electrodes introduced due to the passage of a pre-formed droplet to generate a second droplet at a second pair of electrodes. The device was characterised using image analysis. Droplets with a volume of ~23.5 ± 3.1 nl (i.e.~93% of the volume of pre-formed droplets) were produced on applying a voltage of 500 V. The synchronisation efficiency of the device was 83%. As the device enables self-synchronised production of droplets, it has a potential to increase the reliability and robustness of mixing operations in droplet-based microfluidic devices.     

Synthesis, structure, and spectroscopy of phenylacetylenylene rods incorporating meso-substituted dipyrrin ligands

The synthesis, structure, and spectroscopic characterization of a series of phenylacetylenylene rodlike molecules containing dipyrromethene (dipyrrin) ligands are described. The combination of the phenylacetylenylene groups with the porphyrinogenic dipyrrin moieties results in a rich absorption spectroscopy for these compounds, although the fluorescence of the phenylacetylenylene moiety is quenched by presence of the dipyrrin chelator. The Cu(2+) and Fe(3+) complexes of these ligands have been prepared and three of these compounds have been structurally characterized by using single-crystal X-ray diffraction. Unlike other octahedral metal-dipyrrin complexes described to date, one of the iron complexes demonstrates ideal threefold symmetry in the solid-state. The elongated structure and high symmetry of these complexes suggests the use of these meso-substituted phenylacetylenylene ligands as an interesting class of extended, branched molecules for the construction of supramolecular architectures.