Hairpin helicates: a missing link between double-helicates and trefoil knots

We have prepared a novel ligand in which two qpy metal-binding domains are linked by a polyoxyethylene spacer. The new ligand reacts with copper(ii) salts to form dinuclear double helicates with a hairpin structure. The hairpin complex and a model complex have been structurally characterised. The hairpin structure is formed regioselectively as the head-to-tail (HT) stereoisomer. Detailed electrochemical and spectroelectrochemical studies of the complexes are reported.     

Non-aggregational aromatic oligoamide macrocycles

Attaching peripheral amide groups to the backbone of cyclic aromatic oligoamides 1 leads to new macrocycles 2 that show drastically changed behavior including modest yields of formation and no tendency to aggregate while maintaining a rigid backbone and a defined, guest-binding internal cavity.     

Deciphering aromatic oligoamide foldamer-DNA interactions

Finest selection: Side-chain selective, end-group selective, diastereoselective, and RNA- vs. DNA-selective interactions have been revealed between multiturn helical aromatic amide foldamers having cationic side chains and G-quadruplex aptamers.     

芳香寡聚酰胺大环化合物的合成

通过芳香二胺单体1和二酸酰氯单体2的一步环化反应合成了酰胺键上的氢原子被2,4-二甲氧基苄基部分取代的一系列新型的芳香酰胺八聚体大环化合物3, 这些带有不同R基团环状八聚体的结构得到了核磁、高分辨质谱和MALDI-TOF的确认.     

Model carbyne knots vs ideal knots

The structure and stability of model carbyne knots built from 60 to 120 carbon atoms with 0, 3, 4,., 7 crossings have been estimated by semiempirical AM1 calculations. The calculations have shown an increase of the knot-cycle energy difference (deltaE) with an increasing number of knot crossings and a decrease of deltaE with an increasing number of atoms constituting the molecule. The deltaE changes nonlinearly with the characteristics of the corresponding ideal knots such as the average crossing number (ACN) and the length-to-diameter ratio (L/D). The molecular mechanic strain energy of carbyne knots correlates similarly with ACN and L/D of ideal knots. The calculated energy of the model carbyne knots correlates also with the electrophoretic mobility or sedimentation coefficient of DNA knots. Thus, similarly to characteristics of ideal knots, the energy of carbyne knots is a rather easily available parameter which can be used for further correlations with some characteristics of DNA knots.     

一种带有吡唑啉侧链的低聚酰胺的合成

A oligoamide with pyrazoline segment was designed and synthesized.Its structure was identified by IR,MS and 1HNMR.Fluorescence property of the target compoud in solution(DMF) was studied.The results showed that the strongest emission peak was at 442nm and the half peak width was 64nm and the fluorescence quantum yield(Φ) was 73.9%,which enhanced 13% compared to the simple pyrazoline structural unit's Φ.     

Solution structure of quinoline- and pyridine-derived oligoamide foldamers

The unambiguous elucidation of a new folded structure in solution may prove to be a very challenging task. The NMR protocols developed for solving the solution structures of alpha-peptides have been applied to aliphatic beta- and gamma-peptides but are not directly applicable to aromatic oligomers. In particular, the string of spin systems in an aromatic sequence cannot be reconstituted solely from correlations between protons. For aromatic oligomers, it is shown that the assignment of a large part of the 13C NMR spectrum through HMBC and HSQC experiments allows to unambiguously assign proton NMR spectra and in turn to interpret NOE correlations. This has been implemented both with quinoline- and pyridine-derived oligoamide foldamers, and should be applicable to a wide range of oligomers including various combinations of monomers. The NOE correlations allow the unambiguous solution structure elucidation of helical conformations of oligoamides derived from pyridine and quinoline monomers showing that, in these series, the solution structures correspond very well to the structures observed in the solid state.     

Strong aggregation and directional assembly of aromatic oligoamide macrocycles

Aromatic oligoamide macrocycles exhibit strong preference for highly directional association. Aggregation happens in both nonpolar and polar solvents but is weakened as solvent polarity increases. The strong, directional assembly is rationalized by the cooperative action of dipole-dipole and π-π stacking interactions, leading to long nanotubular assemblies that are confirmed by SEM, TEM, AFM, and XRD. The persistent nanotubular assemblies contain non-collapsible hydrophilic internal pores that mediate highly efficient ion transport observed with these macrocycles and serve as cylindrical sites for accommodating guests such as metal ions.     

Highly conducting transmembrane pores formed by aromatic oligoamide macrocycles

Oligoamide macrocycles 1d and 1e, which carry membrane-compatible side chains and contain a hydrophilic, noncollapsible cavity, were found to mediate high ion flux across a lipid bilayer, as demonstrated by results from (23)Na NMR and planar bilayer conductance measurements. The measured transmembrane single channel currents are very high, rivaling those typically associated with pore-forming protein toxins. The obtained results have demonstrated the promise of developing large, highly conducting channels based on nanopores formed by oligoamide macrocycles.     

Relative helix-helix conformations in branched aromatic oligoamide foldamers

The de novo design and synthesis of large and well-organized, tertiary-like, α-peptidic folded architectures is difficult because it relies on multiple cooperative interactions within and between secondary folded motifs of relatively weak intrinsic stability. The very stable helical structures of oligoamides of 8-amino-2-quinoline carboxylic acid offer a way to circumvent this difficulty thanks to their ability to fold into predictable and stable secondary motifs. Branched architectures comprised of two pairs of tetrameric (1), pentameric (2), or octameric (3) oligomers connected via an ethylene glycol spacer were designed and synthesized. The short spacer holds two helices in close proximity, thus enabling interactions between them. Degrees of freedom allowed in the system are well-defined: the relative P or M handedness of the two helices; the relative orientation of the helix axes; and the gauche or anti conformation of the ethylene spacer. Investigating the structures of 1-3 in the solid state and in solution allowed a detailed picture to be drawn of their conformational preferences and dynamics. The high variability of the solid state structures provides many snapshots of possible solution conformations. Helix-helix handedness communication was evidenced and shown to depend both on solvent and on a defined set of side chains at the helix-helix interface. Interdigitation of the side chains was found to restrict free rotation about the ethylene spacer. One solid state structure shows a high level of symmetry and provides a firm basis to further design specific side chain/side chain directional interactions.     

On amphicheiral knots

Amphicheiral knots with up to 12 crossings are discussed from the perspective of their symmetry properties. By use of an algorithm that involves the development of appropriate vertexbicolored knot graphs, rigidly achiral presentations have been found for all amphicheiral invertible prime knots with up to 10 crossings and for a selected number of such knots with 12 crossings, including 12₁₉₄₄, the first example of an amphicheiral prime knot whoseS _2n diagram is also a reduced diagram. Characteristic properties of wire models of these presentations have been examined. The adjacency matrices of the vertex-bicolored graphs of amphicheiral knots exhibit twofold antisymmetry, and, with the sole exception of 12₄₂₇, all such knots are capable of rigidly antisymmetric presentations.     

A dendron of subphthalocyanine trefoil

The synthesis of a dendron composed of tetrameric subphthalocyanine (SubPc) is accomplished by substituting the chlorine groups with phenoxy groups at the axial positions of SubPc with SubPc-triol. The present molecular design of the SubPc-triol introduces three phenol groups at the peripheral positions of the SubPc macrocycle as a tritopic template to construct SubPc dendrons. The self-polycondensation of SubPc-triol as a ‘divergent’ synthesis only gave a trace amount of the hyperbranched arrays due to poor solubility of the SubPc-triol. In contrast, a ‘convergent’ synthesis with the terminal SubPc improved the solubility throughout the reaction and a tetrameric SubPc dendron was obtained in moderate isolated yield.     

From rods to knots using cyclohexane in smectic liquid crystals

The effects of using cyclohexane as a bulky terminal group or as a linkage between multiple mesogens using 1,4-cyclohexane dicarboxylic acid and 1,3,5-cyclohexane tricarboxylic acid has been investigated. We demonstrate that the diversity of mesomorphism is reduced as the complexity of the molecule increases such that twist grain boundary phases, chiral nematic, ferroelectric and antiferroelectric behaviour are observed in the mono compounds but only ferroelectric behaviour is observed for the trimeric compounds. The electro-optical behaviour is discussed with a focus on the ferroelectric behaviour and the nature of the twist grain boundary phase.     

Multiple hydrogen bonds-mediated formation of supramolecular polysiloxanes based on oligoamide duplexes

Formation of supramolecular polysiloxane polymers was studied by using oligoamide strands 1a, 2a, and 3a bearing multiple hydrogen bonds as association units. According to SEM and TEM studies one polymeric strand associated into supramolecular spherical assemblies via duplex formation. The results demonstrated the effect of such complementary oligoamides upon constructing main-chain supramolecular polymers.     

Hydrogen bonding-induced aromatic oligoamide foldamers as spherand analogues to accelerate the hydrolysis of nitro-substituted anisole in aqueous media

Four intramolecular hydrogen bonding-driven aromatic amide foldamers 2-5 have been designed and synthesized in which a 2-methoxy-3-nitrobenzamide unit was incorporated at the end of the backbone. Kinetic studies in dioxane-water (4:1, v/v) at 60-90 degrees C have revealed that the folded backbone of the oligomers was, like the rigidified spherand, able to complex Li+, Na+, and K+ and, consequently, accelerated the hydrolysis of the nitro-appended anisole unit of the foldamers. Generally, longer foldamers displayed an increased accelerating effect, and LiOH displayed the highest reactivity probably due to the most efficient complexation by the folded oligomers. Addition of excessive potassium chloride substantially reduced the complexing interaction, and the hydrolysis of the longer oligomers became slower than that of the shorter ones due to an increased steric effect. The results indicate that, even in a hot aqueous medium of high polarity, intramolecular hydrogen bonding is still able to induce structurally matched oligomers to generate a preorganized rigidified conformation.     

Mechanism of breakage of liquid threads

Summary The problem of formation and breakage of liquid threads has been discussed from the theoretical point of view. It has been shown that the length of a liquid thread may be limited by two different break processes: brittle cohesive break and break-up into drops due to development of axisymmetrical capillary waves. The actual break moment and the thread length in given conditions are determined by cohesive break affected by development of capillary waves. The effect of waves capillary dominates in low-viscous liquids at low deformation rates — the practically independent cohesive process in high-viscous materials at rapid deformations. The experimental data are qualitatively consistent with the theory and directly confirm the character of break processes. The theory makes also possible the explaining of all the empirical data concerning the spinnability of liquids.

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Zusammenfassung Das Problem der Bildung und des Bruches flüssiger Fäden wurde von theoretischen Gesichtspunkten aus diskutiert. Man kann sehen, daß die Fadenlänge durch zwei verschiedene Prozesse begrenzt ist: den spröden Kohäsionsbruch und den Zerfall in Tropfen infolge von Entwicklung achsensymmetrischer Kapillarwellen. Der tatsächlich auftretende Bruchaugenblick und die Fadenlänge unter gegebenen Bedingungen werden durch denjenigen Prozeß bestimmt, der am schnellsten zum Bruch führt. Kapillarbruch dominiert für niederviskose Flüssigkeiten bei langsameren Verformungsgeschwindigkeiten — der kohäsive Prozeß für hochviskose Materialien bei rascher Deformation. Experimentelle Daten sind qualitativ konsistent mit der Theorie und beweisen unmittelbar Existenz und Art von zweierlei Bruchprozessen. Die Theorie erlaubt auch eine Erklärung aller empirischen Daten, die die Spinnbarkeit von Flüssigkeiten betreffen.

     

Triclosan release from coated polyglycolide threads

Copolymerization of lactide, epsilon-caprolactone, and trimethylene carbonate is performed. The synthesis is focused on obtaining materials with adequate properties for application as a suture coating that could contain an antimicrobial agent like triclosan. An amorphous character, a low glass transition temperature, a moderate susceptibility to degradation, and a hydrophobic nature are the conditions required for the optimal behavior of this coating. These properties can be attained with a copolymer of composition 10:60:30. Triclosan is added to the surface of polyglycolide threads and its release is studied in different media with high-performance liquid chromatography. The influence of the temperature, the diameter of the thread, the initial concentration of the antibacterial agent, and the applied procedure on the incorporation of triclosan is also evaluated. A total release of triclosan is attained after a few days of exposure to a Dulbecco's based medium, whereas equilibrium concentrations are reached when a S?rensen hydrophilic medium is used. Partition and diffusion coefficients are also estimated.     

Extremely strong tubular stacking of aromatic oligoamide macrocycles

As the third-generation rigid macrocycles evolved from progenitor 1, cyclic aromatic oligoamides 3, with a backbone of reduced constraint, exhibit extremely strong stacking with an astoundingly high affinity (estimated lower limit of K _dimer > 10¹³ M^–1 in CHCl₃), which leads to dispersed tubular stacks that undergo further assembly in solution. Computational study reveals a very large binding energy (–49.77 kcal mol^–1) and indicates highly cooperative local dipole interactions that account for the observed strength and directionality for the stacking of 3. In the solid-state, X-ray diffraction (XRD) confirms that the aggregation of 3 results in well-aligned tubular stacks. The persistent tubular assemblies of 3, with their non-deformable sub-nm pore, are expected to possess many interesting functions. One such function, transmembrane ion transport, is observed for 3.