Utilization of the highly environment-sensitive emission properties of rhenium(I) amidodipyridoquinoxaline biotin complexes in the development of biological probes

We report the synthesis and characterization of luminescent rhenium(I) amidodipyridoquinoxaline biotin complexes [Re(CO)3(dpqa)(L)](PF6) (dpqa = 2-(n-butylamido)dipyrido[3,2-f:2',3'-h]quinoxaline; L = 4-(biotinamidomethyl)pyridine (py-4-CH2-NH-biotin) (1), 3-(N-((2-biotinamido)ethyl)amido)pyridine (py-3-CO-NH-en-NH-biotin) (2), 4-(N-((6-biotinamido)hexanoyl)aminomethyl)pyridine (py-4-CH2-NH-cap-NH-biotin) (3)), and their biotin-free counterpart [Re(CO)3(dpqa)(py)](PF6) (py = pyridine (4)). Upon irradiation, these complexes exhibited intense triplet metal-to-ligand charge-transfer (3MLCT) (dpi(Re) --> pi(dpqa)) emission in fluid solutions at 298 K and in alcohol glass at 77 K. However, the emission became much weaker in aqueous buffer, probably due to the interactions of water molecules with the amide substituent of the dpqa ligand. These properties render the complexes good candidates as luminescent probes for hydrophobic media, such as the substrate-binding sites of proteins. The avidin-binding properties of the new biotin complexes have been studied by 4'-hydroxyazobenzene-2-carboxylic acid (HABA) assays, emission titrations, and competitive association and dissociation assays. Most importantly, the complexes showed a profound increase in emission intensities upon binding to avidin. Additionally, we found that the fluorescence of anthracene was quenched by these rhenium(I) complexes, and the 3MLCT emission of the complexes was also quenched by anthracene. On the basis of these findings, new homogeneous assays for biotin using these complexes, avidin, and anthracene-labeled avidin have been designed.     

Organocatalytic Mitsunobu reactions

A catalytic Mitsunobu reaction system is described in which the azo reagent is used as an organocatalyst and iodosobenzene diacetate is used as the stoichiometric oxidant. In this system, iodosobenzene diacetate oxidizes the formed hydrazine byproduct to regenerate the azo reagent. Yields obtained in the catalytic reactions using a variety of carboxylic acids and alcohols were slightly lower than those obtained from corresponding stoichiometric reactions. Both primary and secondary alcohols can be used as substrates in this reaction system, with the secondary alcohols affording products with inverted stereochemistry at the carbinol center.     

Bacterial Cellulose Nanopaper as Reinforcement for Polylactide Composites: Renewable Thermoplastic NanoPaPreg

Bacterial cellulose (BC) is often regarded as a prime candidate nano‐reinforcement for the production of renewable nanocomposites. However, the mechanical performance of most BC nanocomposites is often inferior compared with commercially available polylactide (PLLA). Here, the manufacturing concept of paper‐based laminates is used, i.e., “PaPreg,” to produce BC nanopaper reinforced PLLA, which has been called “nanoPaPreg” by the authors. It is demon­strated that high‐performance nanoPaPreg (v_f = 65 vol%) with a tensile modulus and strength of 6.9 ± 0.5 GPa and 125 ± 10 MPa, respectively, can be fabricated. It is also shown that the tensile properties of nanoPaPreg are predominantly governed by the mechanical performance of BC nanopaper instead of the individual BC nanofibers, due to difficulties impregnating the dense nanofibrous BC network.

     

Head-to-tail dimerization and organogelating properties of click peptidomimetics

Click triazole-based oligopeptides 1-3 were found to self-dimerize (K(dim) ≈ 10-680 M(-1)) in a head-to-tail fashion based on (1)H variable concentration, 2D, and H/D exchange NMR, VPO, CD, FT-IR studies and Gaussian 03 simulations. The dimerization constant K(dim) was shown to increase with increasing number of the amino acid units. Within the same oligomeric series, the K(dim) value is strongly affected by the size of the C-terminal end group. The tripeptides 2 are also excellent organogelators of aromatic solvents.     

Scalar coupling across [C-H···F-C] interactions in (σ-aryl)-chelating post-metallocenes

The nature and importance of C-H···F-C interactions is a topical yet controversial issue, and the development of spectroscopic methods to probe such contacts is therefore warranted. A series of Group 4 bis(benzyl) complexes supported by (σ-aryl)-2-phenolate-6-pyridyl [O,C,N-R(1)] ligands bearing a fluorinated R(1) group (CF(3) or F) in the vicinity of the metal has been prepared. The X-ray crystal structure of the CF(3)-substituted Hf derivative features intramolecular C-H···F-C and Hf···F-C contacts. All complexes have been characterized by multinuclear NMR spectroscopy. The (1)H and (13)C NMR spectra of [M(O,C,N-CF(3))(CH(2)Ph)(2)] derivatives display coupling (assigned to (1h)J(HF) and (2h)J(CF) for Ti; (3)J(HF) and (2)J(CF) (through M···F) for Hf and Zr) between the benzyl CH(2) and CF(3) moieties. [(1)H,(19)F]-HMBC NMR experiments have been performed for the M-[O,C,N-R(1)] complexes and their [O,N,C] counterparts, revealing significant scalar coupling across the C-H···F-C interactions for Ti-[O,C,N] and [O,N,C] species.     

Structure of planar integral self‐affine tilings

For a self‐affine tile in $\mathbf {R}^2$ generated by an expanding matrix $A\in M_2(\mathbf {Z})$ and an integral consecutive collinear digit set ${\mathcal D}$, Leung and Lau [Trans. Amer. Math. Soc. 359 , 3337–3355 (2007).] provided a necessary and sufficient algebraic condition for it to be disklike. They also characterized the neighborhood structure of all disklike tiles in terms of the algebraic data A and ${\mathcal D}$. In this paper, we completely characterize the neighborhood structure of those non‐disklike tiles. While disklike tiles can only have either six or eight edge or vertex neighbors, non‐disklike tiles have much richer neighborhood structure. In particular, other than a finite set, a Cantor set, or a set containing a nontrivial continuum, neighbors can intersect in a union of a Cantor set and a countable set.     

Collective coordinates and the mechanism for conformational transitions of complex molecules

Reduction of dimensionality is crucial for the deeper understanding of the mechanism for large-amplitude conformational transitions of complex molecules. By taking up a six-atomcluster as an illustrative example, we present a general methodology to understand conformational transitions of molecules in terms of the low-dimensional dynamics of molecular gyration radii. The dynamics of gyration radii is generally governed by the interplay between the ordinary potential force and a dynamical force called the internal centrifugal force. We show that the internal centrifugal force can be more important than the original potential barrier and gives rise to a new dynamical barrier that truly dominates the conformational transitions of the system. This kind of dynamical effect should be crucially important in a wide class of molecular reaction dynamics. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ion-implanted treatment of (Ba,Sr)TiO3 films for DRAM applications

The effects of ion implantation on the properties of spin-on sol–gel Ba_0.7Sr_0.3TiO₃ (BST) thin films were studied by implanted Ar⁺, N⁺, and F⁺ doses. The F⁺-implanted BST samples present leakage current density <10⁻⁶ A/cm² at 2.5 V and dielectric constant 450. The leakage current of F⁺-implanted BST samples was reduced about one order of magnitude as compared with that of samples with implanted Ar⁺, N⁺ or without implantation. The thickness shrinkage from 135 to 115 nm was observed in F⁺-implanted BST films (before annealing treatment) and a respective increase in the refractive index from 1.84 to 2.05 was measured. After annealing the implanted samples, the changes of thickness and refractive index depend on the concentration of implanted dose. Based on an infrared transmission study of the samples we suggest that the ion-implanted samples with smaller dose (5×10¹⁴ cm⁻²) have fewer −OH contaminants than the non-implanted or implanted samples with the larger doses (1×10¹⁵ cm⁻²). Based on the results presented, we conclude that suitable ion implantation densifies the spin-on sol–gel BST films and reduces the −OH contaminants in the films.     

Giant magnetostriction materials

One of the significant technical developments in magnetism of the early 1970's was the discovery of a new class of rare earth intermetallic compounds, the RFe₂ Laves phases, which were found to exhibit room temperature magnetostrictive strains approaching 2 × 10⁻³, an order of magnitude larger than any previously known. Since that time both the fundamental and technical properties of these materials have been of intense interest, and they remain the subject of active research even today. The large strains available are useful in such applications as production of high amplitude, low frequency sound waves in water, certain types of strain gages, vibration compensation and compensation for temperature induced strains in large laser mirrors. Because the performance of these materials depends critically on such fundamental properties as the magnetic anisotropy, magnetization and grain orientation of the material, there has been a very strong interplay between fundamental studies and applications. In this article we briefly review the fundamental magnetic and magnetostrictive properties of the RFe₂ Laves phases, focusing especially on the complex behavior of the anisotropy and the success of crystal field theory in explaining it. We also present neutron measurements of magnetic excitation spectra and explain how they provide an understanding of the remarkable success of mean field theory for these systems.