Oligofunctional amphiphiles featuring geometric core group preorganization: synthesis and study of Langmuir and Langmuir-Blodgett films

Based on the principle of supramolecular preorganization, a new type of oligofunctional amphiphile, of which compounds 1-4 are representative structures, has been designed and synthesized. The typical feature of their structure is a highly rigid and geometrically well-defined central unit composed of ethynylene substituted aromatic spacers with different numbers of amphiphilic segment groups (also of a rigid geometric design) attached to it. The molecules form well-defined Langmuir films when spread from a solution at the air/water interface or when a 10(-4) M aqueous CaCl2 solution was used as the subphase. By analysis of the surface pressure-surface area (pi-A) isotherms, information on the packing behavior and orientation of the amphiphilic molecules depending on the molecular structure could be obtained. Morphological characterization of the dynamic process of monolayer compression at the air/water interface was carried out by Brewster angle microscopy, illustrating several phase states visualized as snap shots. Thin monolayer films produced on a 10(-4) M aqueous CaCl2 subphase can be transferred to a mica solid support by the Langmuir-Blodgett technique. Tapping mode atomic force microscopy reveals a surface topography of the monofilms composed of 1 and 3 that differ in roughness and also in the properties of elasticity, hardness and adhesive strength. X-Ray crystal structure analysis of three relevant intermediate compounds of the synthesis were successfully determined giving an indication of the potential structural features inherent in the new amphiphiles.     

Four-color fluorescence correlation spectroscopy realized in a grating-based detection platform

We have developed a filterless multicolor detection unit for fluorescence correlation spectroscopy (FCS). This grating-based setup is continuously tunable for multicolor separation and is thus a powerful alternative to the classical cascade of dichroic mirrors and filters. Our tailored platform allows for accommodation of up to 15 detection channels covering the entire visible spectral range. As a proof of principle, we successfully demonstrate simultaneous FCS of four distinct fluorescent quantum dot species being mixed in aqueous solution. Grating-based detection allows for spectral high-resolution FCS in a stable and compact setup and is a feasible tool for quantitative investigation of complexbiomolecular dynamics on a single molecule level.     

Convergence Groups, Hausdorff Dimension, and a Theorem of Sullivan and Tukia

We show that a discrete, quasiconformal group preserving ⁿ has the property that its exponent of convergence and the Hausdorff dimension of its limit set detect the existence of a non-empty regular set on the sphere at infinity to ⁿ . This generalizes a result due separately to Sullivan and Tukia, in which it is further assumed that the group act isometrically on ⁿ , i.e. is a Kleinian group. From this generalization we are able to extract geometric information about infinite-index subgroups within certain of these groups.     

A simple approach to sensor discovery and fabrication on self-assembled monolayers on glass

Self-assembled monolayers (SAMs) on glass were used as a platform to sequentially deposit fluorophores and small molecules for ion sensing. The preorganization provided by the surface avoids the need for complex receptor design, allowing for a combinatorial approach to sensing systems based on small molecules. The resulting libraries are easily measured and show varied responses to a series of both cations and anions. This technology is transferable from the macro- to the microscale both via microcontact printing (microCP), where the fluorophore is printed onto a glass surface, and via direct attachment of the fluorophore to microchannel walls. The ease of miniaturization of this technology may make the generation of a wide variety of simple yet efficient microarrays possible.     

A zero topological entropy map with recurrent points not

We show that there is a continuous map of the unit interval into itself of type which has a trajectory disjoint from the set of recurrent points of , but contained in the closure of . In particular, is not closed. A function of type , with nonclosed set of recurrent points, was found by H. Chu and J. Xiong [Proc. Amer. Math. Soc. 97 (1986), 361-366]. However, there is no trajectory contained in , since any point in is eventually mapped into . Moreover, our construction is simpler.

We use to show that there is a continuous map of the interval of type for which the set of recurrent points is not an set. This example disproves a conjecture of A. N. Sharkovsky et al., from 1989. We also provide another application of .

     

Low‐bandgap donor–acceptor copolymers with 4,6‐bis(3′‐(2‐ethylhexyl)thien‐2′‐yl)thieno[3,4‐c][1,2,5]thiadiazole: synthesis,optical, electrochemical,and photovoltaic properties

Two new low‐bandgap alternating copolymers (CEHTF and CEHTP) consisting of 4,6‐bis(3′‐(2‐ethylhexyl)thien‐2′‐yl)thieno[3,4‐c][1,2,5] thiadiazole and 9,9‐bis(2‐ethylhexyl)fluorene or 2,5‐bis(isopentyloxy)benzene were synthesized by Suzuki coupling reaction of corresponding comonomers. Their optical, electrochemical, and photovoltaic (PV) properties were studied and are reported. Both the copolymers exhibited long‐wavelength absorption covering the whole visible spectral region, which is in CEHTP thin films extended up to near infrared region, ambipolar redox properties, and electrochromism. High‐electron affinities and low‐optical bandgap values, 1.37 and 1.15 eV, were determined for CEHTF and CEHTP, respectively. PV devices with bulk heterojunction made of blends of copolymers and fullerene derivative [6,6]‐phenyl‐C⁶¹‐butyric acid methyl ester ([60]PCBM) were prepared and characterized. Effects of intramolecular charge transfer strength and side‐chain nature and length on photophysical properties are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Probing the Hydrogen Bonding Structure in the Rieske Protein

The use of the far‐infrared spectral range presents a novel approach for analysis of the hydrogen bonding in proteins. Here it is presented for the analysis of Fe? S vibrations (500–200 cm^?1) and of the intra‐ and intermolecular hydrogen bonding signature (300–50 cm^?1) in the Rieske protein from Thermus thermophilus as a function of temperature and pH. Three pH values were adequately chosen in order to study all the possible protonation states of the coordinating histidines. The Fe? S vibrations showed pH‐dependent shifts in the FIR spectra in line with the change of protonation state of the histidines coordinating the [2Fe? 2S] cluster. Measurements of the low‐frequency signals between 300 and 30 K demonstrated the presence of a distinct overall hydrogen bonding network and a more rigid structure for a pH higher than 10. To further support the analysis, the redox‐dependent shifts of the secondary structure were investigated by means of an electrochemically induced FTIR difference spectroscopic approach in the mid infrared. The results confirmed a clear pH dependency and an influence of the immediate environment of the cluster on the secondary structure. The results support the hypothesis that structure‐mediated changes in the environment of iron? sulfur centers play a critical role in regulating enzymatic catalysis. The data point towards the role of the overall internal hydrogen bonding organization for the geometry and the electronic properties of the cluster.