Coupling Titanium and Chromium Catalysis in a Reaction Network for the Reprogramming of [BH4]− as Electron Transfer and Hydrogen Atom Transfer Reagent for Radical Chemistry

We describe a unique catalytic system with an efficient coupling of Ti- and Cr-catalysis in a reaction network that allows the use of [BH₄]⁻ as stoichiometric hydrogen atom and electron donor in catalytic radical chemistry. The key feature is a relay hydrogen atom transfer from [BH₄]⁻ to Cr generating the active catalysts under mild conditions. This enables epoxide reductions, regiodivergent epoxide opening and radical cyclizations that are not possible with cooperative catalysis with radicals or by epoxide reductions via Meinwald rearrangement and ensuing carbonyl reduction. No typical S_N2-type reactivity of [BH₄]⁻ salts is observed.     

Pentacene nanorails on Au(110)

We studied the molecular orientation of pentacene monolayer phases on the Au(110) surface by means of near-edge X-ray absorption spectroscopy at the carbon K-shell and scanning tunneling microscopy. The highest coverage phase, displaying a (6 x 8) symmetry, is found to be formed by two types of differently oriented molecules mimicking regular arrays of nanorails. Flat-lying molecules, aligned side-by-side with the long molecular axis along the [001] direction, form long crosstie chains extending in the [110] direction. In between the adjacent flat chains, additional molecules, tilted by 90 degrees around their molecular axis, line up head-to-tail into rails extending along [110]. These molecules are very weakly hybridized with the substrate, as indicated by their lowest unoccupied molecular orbitals, which closely resemble those of the free molecule. The nanorail structure is found to be stable up to 420 K in vacuum and to also remain in place after exposure to air, thus being a template well suited for further self-assembly of organic heterostructures. The tilted quasi-free molecules open the possibility for an optimal lateral pi-coupling to other molecules or molecular assemblies.     

Micrometer and nanometer scale patterning using the photo-fries rearrangement: toward selective execution of molecular transformations with nanoscale spatial resolution

The photolithographic modification of monolayers provides a versatile and powerful means of fabricating functionalized nanostructured surfaces. In this contribution, we present photosensitive thiol-bearing aryl ester groups which are capable of undergoing the so-called photo-Fries rearrangement to yield hydroxyketones. Phenyl 16-mercaptohexadecanoate was prepared by a three-step synthesis. This molecule undergoes a photoisomerization reaction upon illumination with UV light at ca. 250 nm. Subsequently this molecule was applied as a self-assembled monolayer on gold. Following photochemical modification, the adsorbates were selectively derivatized to yield amino-functionalized surfaces using a simple two-step reaction. This reaction was monitored by X-ray photoelectron spectroscopy and contact angle measurements and friction force microscopy. Micrometer-scale patterned surfaces were produced using a contact mask in conjunction with a frequency-doubled argon ion laser (lambda=244 nm). Near-field optical exposure was carried out by coupling the laser to a scanning near-field optical microscope and yielded nanometer-scale resolution. Following derivatization, the resulting structures were analyzed by friction force microscopy. Clear contrast was observed in the friction signal following surface modification.     

Synthesis and optical properties of all-trans-oligodiacetylenes

A new series of pure and highly soluble oligodiacetylenes (ODAs) was synthesized in high yield and on a multi-milligram scale by a sequence of Sonogashira reactions with a strongly reduced level of homocoupling. The lambda(max) and epsilon(max) of these ODAs show an increase with both chain elongation and solvent polarity. A plot of lambda(max) absorption versus 1/CL (CL=conjugation length) was shown to be linear. The lambda(max) converges to 435 nm for the longest members of the series at micromolar concentration. This reveals that the longest wavelength absorption observed for PDA chains (lambda(max) up to 700 nm) is due to aggregation effects. The fluorescence quantum yield increased from monomer to trimer and decreased for longer ODAs. A similar trend is found for the lifetime of fluorescence with a maximum of 600 ps for the trimer. The observed linearity of the rotational correlation time with the oligomer length implies that the ODA chains in solution lack significant geometrical changes. This implies that the ODAs in solution are fully stretched molecular rods of up to 4 nm in length.     

Synthesis, resolution, and absolute configuration of difunctionalized Tröger's base derivatives

Two racemic derivatives of Tr?ger's base, the 2,8-diboronic acid ester 6 and the 3,9-dibromo-substituted derivative 5, were synthesized and successfully resolved by HPLC on a chiral stationary Whelk-01 phase on a semipreparative scale, thereby giving rise to both enantiomers in a pure form. These functionalized C(2)-symmetric building blocks are valuable precursors for a variety of further applications. Their absolute configurations were determined by comparison of their quantum chemically calculated CD and UV/Vis spectra with the experimental ones and were independently confirmed by X-ray diffraction analysis.     

Poly(norbornene)s as matrix materials for platinum tetrakis(pentafluorophenyl)porphyrin based optical oxygen sensors

A set of poly(norbornenes) was prepared using ring opening metathesis polymerization (ROMP) and used as matrix material for the preparation of optical oxygen sensor layers based on platinum tetrakis(pentafluorophenyl)porphyrin (PtTFPP) as the sensitive dye. Different polymers were prepared and investigated in order to retrieve information on the influence of the anchor group and the side chain attached to the polymer backbone on their performance as matrix material for the dye. Bulky side groups increased the oxygen permeability through ROM polymer layers, especially when the bulky group was directly attached via an anchor group to the polymer backbone without any aliphatic spacer in between. Sensor layers made of poly(endo,exo[2.2.1]bicyclo-5-heptene-2,3-dicarboxyclic acid di-tert-butylester) and PtTFPP exhibited the highest τ₀/τ ratio and responded strongly to small amounts of oxygen.     

Electrode commutation sequence for honeycomb arrangement of electrodes in electrochemotherapy and corresponding electric field distribution

Electrochemotherapy is a treatment based on combination of chemotherapeutic drug and electroporation. It is used in clinics for treatment of solid tumours. For electrochemotherapy of larger tumours multiple needle electrodes were already suggested. We developed and tested electrode commutation circuit, which controls up to 19 electrodes independently. Each electrode can be in one of three possible states: on positive or negative potential or in the state of high impedance. In addition, we tested a pulse sequence using seven electrodes for which we also calculated electric field distribution in tumour tissue by means of finite-elements method. Electrochemotherapy, performed by multiple needle electrodes and tested pulse sequence on large subcutaneous murine tumour model resulted in tumour growth delay and 57% complete responses, thus demonstrating that the tested electrode commutation sequence is efficient.     

Nitric oxide sensor based on carbon fiber covered with nickel porphyrin layer deposited using optimized electropolymerization procedure

Electropolymerization regime of meso-tetrakis(3-methoxy-4-hydroxyphenyl) porphyrin is optimized to yield films possessing both electrocatalytical and permselective properties towards nitric oxide oxidation. The sensor composed of electrochemically oxidized carbon fiber, covered solely with nickel porphyrin derivative layer electropolymerized using our method, is characterized by high selectivity towards nitrite (1:600), ascorbate (1:8000) and dopamine (>1:80), determined by constant potential amperometry at 830 mV (vs. Ag/AgCl). Selectivity for ascorbate and dopamine as well as detection limit for NO (1.5 nM at S/N=3) is 5-10 times better than parameters usually reported for Nafion coated porphyrinic sensors. Nafion coating can further enhance selectivity properties as well as aids to the stability of the sensors' responses.