Two-photon absorption in aqueous micellar solutions

Addition of the surfactant sodium dodecyl sulfate at concentrations above the critical micelle concentration increases the fluorescence quantum yield and the two-photon absorption cross-section of charged [2.2]paracyclophane chromophores containing pairs of D-pi-D chromophores. The resulting spectra in the micellar solutions are very similar to those obtained for neutral isostructural analogues in toluene. The measured etadelta values are 1300 GM for 1C and 1920 GM for 2C, which are comparable or larger to those in toluene. These results highlight possible misleading interpretation of two-photon-induced emission for evaluating the concentration of labeled substrates used in two-photon microscopy and provide guidelines for designing molecular structures with optimized two-photon action cross-sections in water.     

Factorization of proper holomorphic maps on irreducible bounded symmetric domains of rank≥2

We obtain rigidity results on arbitrary proper holomorphic maps F from an irreducible bounded symmetric domain Ω of rank ≥2 into any complex space Z. After lifting to the normalization of the subvariety F (Ω) Z, we prove that F must be the canonical projection map to the quotient space of Ω by a finite group of automorphisms. The approach is along the line of the works of Mok and Tsai by considering radial limits of bounded holomorphic functions derived from F and proving that proper holomorphic maps between bounded symmetric domains preserve certain totally geodesic subdomains. In contrast to the previous works, in general we have to deal with multivalent holomorphic maps for which Fatou’s theorem cannot be applied directly. We bypass the difficulty by devising a limiting process for taking radial limits of correspondences arising from proper holomorphic maps and by elementary estimates allowing us to define distinct univalent branches of the underlying multivalent map on certain subsets. As a consequence of our rigidity result, with the exception of Type-IV domains, any proper holomorphic map f : Ω→ D of Ω onto a bounded convex domain D is necessarily a biholomorphism. In the exceptional case where Ω is a Type-IV domain, either f is a biholomorphism or it is a double cover branched over a totally geodesic submanifold which can be explicitly described.     

Molecular Design of a New Diboronic Acid for the Electrohydrodynamic Monitoring of Glucose

A new dicationic diboronic acid structure, DBA2+ , was designed to exhibit good affinity (K_d≈1 mm ) and selectivity toward glucose. Binding of DBA2+ to glucose changes the pK_a of DBA2+ from 9.4 to 6.3, enabling opportunities for detection of glucose at physiological pH. Proton release from DBA2+ is firmly related to glucose concentrations within the physiologically relevant range (0–30 mm ), as verified by conductimetric monitoring. Negligible interference from other sugars (for example, maltose, fructose, sucrose, lactose, and galactose) was observed. These results demonstrate the potential of DBA2+ for selective, quantitative glucose sensing. The nonenzymatic strategy based on electrohydrodynamic effects may enable the development of stable, accurate, and continuous glucose monitoring platforms.     

A Broad Light-Harvesting Conjugated Oligoelectrolyte Enables Photocatalytic Nitrogen Fixation in a Bacterial Biohybrid

We report a rationally designed membrane-intercalating conjugated oligoelectrolyte (COE), namely COE-IC , which endows aerobic N₂-fixing bacteria Azotobacter vinelandii with a light-harvesting ability that enables photosynthetic ammonia production. COE-IC possesses an acceptor-donor-acceptor (A-D-A) type conjugated core, which promotes visible light absorption with a high molar extinction coefficient. Furthermore, COE-IC spontaneously associates with A. vinelandii to form a biohybrid in which the COE is intercalated within the lipid bilayer membrane. In the presence of L-ascorbate as a sacrificial electron donor, the resulting COE-IC /A. vinelandii biohybrid showed a 2.4-fold increase in light-driven ammonia production, as compared to the control. Photoinduced enhancement of bacterial biomass and production of L-amino acids is also observed. Introduction of isotopically enriched ¹⁵N₂ atmosphere led to the enrichment of ¹⁵N-containing intracellular metabolites, consistent with the products being generated from atmospheric N₂.     

Chemical imaging of single 4,7,12,15-tetrakis[2.2]paracyclophane by spatially resolved vibrational spectroscopy

Single 4,7,12,15-tetrakis[2.2]paracyclophane were deposited on NiAl(110) surface at 11 K. Two adsorbed species with large and small conductivities were detected by the scanning tunneling microscope (STM). Their vibrational properties were investigated by inelastic electron tunneling spectroscopy (IETS) with the STM. Five vibrational modes were observed for the species with the larger conductivity. The spatially resolved vibrational images for the modes show striking differences, depending on the coupling of the vibrations localized on different functional groups within the molecule to the electronic states of the molecule. The vibrational modes are assigned on the basis of ab initio calculations. No IETS signal is resolved from the species with the small conductivity.     

Novel organic materials through control of multichromophore interactions

The function of organic semiconducting and light-harvesting materials depends on the organization of the individual molecular components. Our group has tackled the problem of through-space delocalization via the design and synthesis of bichromphoric pairs held in close proximity by the [2.2]paracyclophane core. The linear and nonlinear optical properties of these molecules provide a challenge to theory. They are also useful in delineating the problem of intermolecular contacts in molecular conductivity measurements. Another area of research described here concerns conjugated polyelectrolytes. These macromolecules combine the properties of organic semiconductors and conventional polyelectrolytes. We have used these materials in the development of optically amplified biosensors and have also incorporated them into organic optoelectronic devices. Of particular interest to us is to derive useful structure/property relationships via molecular design that address important basic scientific problems and technological challenges.