Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

Functionalized Silver-Ion-Mediated α-dC/β-dC Hybrid Base Pairs with Exceptional Stability: α-d-5-Iodo-2′-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Silver-mediated α-dC–Ag⁺–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T_m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag⁺–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.     

Sodium trichloro­methane­sulfonate monohydrate

Sodium trichloro­methane­sulfonate monohydrate, Na⁺·CCl₃SO₃⁻·H₂O, crystallizes in P2₁/a with all the atoms located in general positions. The trichloro­methane­sulfonate (trichlate) anion consists of pyramidal SO₃ and CCl₃ groups connected via an S—C bond in a staggered conformation with approximate C_3v symmetry. The water mol­ecule is hydrogen bonded to the sulfonate O atoms, with one water H atom forming weak bifurcated O—H⋯O hydrogen bonds to two different trichlate ions. Two water O atoms and three O atoms from different SO₃ groups form a square‐pyramidal arrangement around the sodium ion.     

Design and synthesis of Ru(II-bipyridyl-containing conjugated polymers

A series of novel π-conjugated polymers containing ruthenium bipyridine complexes was synthesized by a cross-coupling reaction and characterized. These polymers exhibit absorption maxima around 330–350 nm (π-π*) and 460–500 nm metal-to-ligand charge transfer (MLCT), respectively. They are soluble in common organic solvents, and all polymers can be converted into transparent films. We investigated the influence of different donating and acceptor diethynylarenes of the ultraviolet-visible spectra. The oxidation potential, which was measured by cyclic- and square-wave voltametry, showed a typical Ru^2+/3+ exhibited at 1.25 V versus the saturated calomel electrode. The polymers were further characterized with photoluminescence measurements. When excited at 442 nm ( 11a ), the polymer exhibited an emission peak at 690 nm. This peak was attributed to the MLCT states. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 722–732, 2004     

Non-perturbative approach to high-index-contrast variations in electromagnetic systems

We present a method that formally calculates exact frequency shifts of an electromagnetic field for arbitrary changes in the refractive index. The possible refractive index changes include both anisotropic changes and boundary shifts. Degenerate eigenmode frequencies pose no problems in the presented method. The approach relies on operator algebra to derive an equation for the frequency shifts, which eventually turn out in a simple and physically sound form. Numerically the equations are well-behaved, easy implementable, and can be solved very fast. Like in perturbation theory a reference system is first considered, which then subsequently is used to solve another related, but different system. For our method precision is only limited by the reference system basis functions and the error induced in frequency is of second order for first-order basis set error. As an example we apply our method to the problem of variations in the air-hole diameter in a photonic crystal fiber.     

On the classification of all self-dual additive codes over GF(4) of length up to 12

We consider additive codes over GF(4) that are self-dual with respect to the Hermitian trace inner product. Such codes have a well-known interpretation as quantum codes and correspond to isotropic systems. It has also been shown that these codes can be represented as graphs, and that two codes are equivalent if and only if the corresponding graphs are equivalent with respect to local complementation and graph isomorphism. We use these facts to classify all codes of length up to 12, where previously only all codes of length up to 9 were known. We also classify all extremal Type II codes of length 14. Finally, we find that the smallest Type I and Type II codes with trivial automorphism group have length 9 and 12, respectively.     

Slow-light enhanced optical detection in liquid-infiltrated photonic crystals

Slow-light enhanced optical detection in liquid-infiltrated photonic crystals is theoretically studied. Using a scattering-matrix approach and the Wigner–Smith delay time concept, we show that optical absorbance benefits both from slow-light phenomena as well as a high filling factor of the energy residing in the liquid. Utilizing strongly dispersive photonic crystal structures, we numerically demonstrate how liquid-infiltrated photonic crystals facilitate enhanced light–matter interactions, by potentially up to an order of magnitude. The proposed concept provides strong opportunities for improving existing miniaturized absorbance cells for optical detection in lab-on-a-chip systems.     

The first encapsulation of hydroxynitrile lyase from Hevea brasiliensis in a sol-gel matrix

A straightforward process for the encapsulation of HbHNL under low methanol conditions has been developed. By adding a sol, prepared by hydrolysis of TMOS/MTMS at pH 2.8 with continuous removal of methanol, to a stirred solution of the enzyme in a buffer at pH 6.5, at least 65% of the activity of the free enzyme could be recovered after the encapsulation. The aquagels were successfully used in the synthesis of (S)-cyanohydrins.