From macro- to nanoscopic templating with nanographenes

A hexa-peri-hexabenzocoronene carrying six long, branched alkyl chains has been processed in nano- and macroscopic pore templates. An extraordinary self-organization of this material was observed within macroscopically large glass capillaries after cooling from the isotropic phase. Thereby, the columnar structures were long-range aligned along the capillary axis over several centimeters. This behavior was explained by the pronounced directional self-assembly of the molecules, whereby the curvature effect of the capillary was negligible. The processing in nanoscopic pores of an inorganic membrane yielded an improved supramolecular organization. It was possible to remove the inorganic template and to obtain bundles and single nanorods. The templating over different dimensions opens a variety of potential applications.     

Rational design, synthesis, and spectroscopic and photophysical properties of a visible-light-excitable, ratiometric, fluorescent near-neutral pH indicator based on BODIPY

A visible-light-excitable, ratiometric, brightly fluorescent pH indicator for measurements in the pH range 5-7 has been designed and synthesized by conjugatively linking the BODIPY fluorophore at the 3-position to the pH-sensitive ligand imidazole through an ethenyl bridge. The probe is available as cell membrane permeable methyl ester 8-(4-carbomethoxyphenyl)-4,4-difluoro-3-[2-(1H-imidazol-4-yl)ethenyl]-1,5,7-trimethyl-3a,4a-diaza-4-bora-s-indacene (I) and corresponding water-soluble sodium carboxylate, sodium 8-(4-carboxylatophenyl)-4,4-difluoro-3-[2-(1H-imidazol-4-yl)ethenyl]-1,5,7-trimethyl-3a,4a-diaza-4-bora-s-indacene (II). The fluorescence quantum yield Φ(f) of ester I is very high (0.8-1.0) in the organic solvents tested. The fluorescence lifetime (ca. 4 ns) of I in organic solvents with varying polarity/polarizability (from cyclohexane to acetonitrile) is independent of the solvent with a fluorescence rate constant k(f) of 2.4×10(8) s(-1). Probe I is readily loaded in the cytosol of live cells, where its high fluorescence intensity remains nearly constant over an extended time period. Water-soluble indicator II exhibits two acid-base equilibria in aqueous solution, characterized by pK(a) values of 6.0 and 12.6. The Φ(f) value of II in aqueous solution is high: 0.6 for the cationic and anionic forms of the imidazole ligand, and 0.8 for neutral imidazole. On protonation-deprotonation in the near-neutral pH range, UV/Vis absorption and fluorescence spectral shifts along with isosbestic and pseudo-isoemissive points are observed. This dual-excitation and dual-emission pH indicator emits intense green-yellow fluorescence at lower pH and intense orange fluorescence at higher pH. The influence of ionic strength and buffer concentration on the absorbance and steady-state fluorescence of II has also been investigated. The apparent pK(a) of the near-neutral acid-base equilibrium determined by spectrophotometric and fluorometric titration is nearly independent of the added buffer and salt concentration. In aqueous solution in the absence of buffer and in the pH range 5.20-7.45, dual exponential fluorescence decays are obtained with decay time τ(1)=4.3 ns for the cationic and τ(2)=3.3 ns for the neutral form of II. The excited-state proton exchange of II at near-neutral pH becomes reversible on addition of phosphate (H(2)PO(4)(-)/HPO(4)(2-)) buffer, and a pH-dependent change of the fluorescence decay times is induced. Global compartmental analysis of fluorescence decay traces collected as a function of pH and phosphate buffer concentration was used to recover values of the deactivation rate constants of the excited cationic (k(01)=2.4×10(8) s(-1)) and neutral (k(02)=3.0×10(8) s(-1)) forms of II.     

Adsorption isotherm and other properties of methane in zeolite A from an intermolecular potential derived from ab initio calculations

A classical Lennard-Jones potential is derived from a fit to the ab initio energies obtained from an all-electron mixed-basis calculation for methane in zeolite LTA. The potential predicts the heat of adsorption, adsorption isotherm, and self-diffusivity of methane in excellent agreement with experiment. This study suggests, for the first time, that ab initio energies-in addition to experimental data-can form a good basis for derivation of accurate classical potentials between organic and inorganic elements.     

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO₃-BaF₂-WO₃ ternary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L_I and L_III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO₆) and that these glasses are free of tungstate tetrahedra (WO₄).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO₃ increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO₆ octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O⁻ and WO terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO₃ concentrated samples (?30% molar) due to the formation of WO₆ clusters.     

1,2,3,4-tetrahydro-8-hydroxymanzamines, alkaloids from two different haplosclerid sponges

The isolation and characterization of two new sponge alkaloids, 1,2,3,4-tetrahydro-2-N-methyl-8-hydroxymanzamine A (2) and 1,2,3,4-tetrahydro-8-hydroxymanzamine A (3), is described. These compounds were obtained from Papua New Guinea sponges of the genera Petrosia and Cribochalina, which are in different families of the order Haplosclerida. These new manzamines are close in structure to 8-hydroxymanzamine (4) recently reported from Pachypellina, a Haplosclerid sponge belonging to a different family than that of the two preceding sponges. The cytotoxicity of 2 is described and the biogenetic relationship of 2 or 3 to manzamine A (1) and to nine other related polycyclic diamine and one monoamine type alkaloids is described.     

A biotechnological process involving filamentous fungi to produce natural crystalline vanillin from maize bran

A new process involving the filamentous fungi Aspergillus niger and Pycnoporus cinnabarinus has been designed for the release of ferulic acid by enzymic degradation of a cheap and natural agricultural byproduct (autoclaved maize bran) and its biotransformation into vanillic acid and/or vanillin with a limited number of steps. On the one hand, the potentialities of A. niger I-1472 to produce high levels of polysaccharide-degrading enzymes including feruloyl esterases and to transform ferulic acid into vanillic acid were successfully combined for the release of free ferulic acid from autoclaved maize bran. Then vanillic acid was recovered and efficiently transformed into vanillin by P. cinnabarinus MUCL 39533, since 767 mg/L of biotechnologic vanillin could be produced in the presence of cellobiose and XAD-2 resin. On the other hand, 3-d-old high-density cultures of P. cinnabarinus MUCL39533 could be fed with the autoclaved fraction of maize bran as a ferulic acid source and a. niger I-1472 culture filtrate as an extracellular enzyme source. Under these conditions, P. cinnabarinus MUCL39533 was shown to directly biotransform free ferulic acid released from the autoclaved maize bran by A. niger I-1472 enzymes into 584 mg/L of vanillin. These processes, involving physical, enzymic, and fungal treatments, permitted us to produce crystallin vanillin from autoclaved maize bran without any purification step.     

Ceramic microreactors for heterogeneously catalysed gas-phase reactions

The high surface to volume ratio of microchannel components offers many advantages in micro chemical engineering. It is obvious, however, that the reactor material and corrosion phenomena play an important role when applying these components. For chemical reactions at very high temperatures or/and with corrosive reactants involved, microchannel components made of metals or polymers are not suited. Hence, a modular microreactor system made of alumina was developed and fabricated using a rapid prototyping process chain. With exchangeable inserts the system can be adapted to the requirements of various reactions. Two heterogeneously catalysed gas-phase reactions (oxidative coupling of methane, isoprene selective oxidation to citraconic anhydride) were investigated to check the suitability of the system at temperatures of up to 1000 degrees C. Apart from the high thermal and chemical resistance, the lack of any blind activity was found to be another advantage of ceramic components.     

Biodegradable High-Density Polyethylene-like Material

We report a novel polyester material generated from readily available biobased 1,18-octadecanedicarboxylic acid and ethylene glycol possesses a polyethylene-like solid-state structure and also tensile properties similar to high density polyethylene (HDPE). Despite its crystallinity, high melting point (T_m=96 °C) and hydrophobic nature, polyester-2,18 is subject to rapid and complete hydrolytic degradation in in vitro assays with isolated naturally occurring enzymes. Under industrial composting conditions (ISO standard 14855-1) the material is biodegraded with mineralization above 95 % within two months. Reference studies with polyester-18,18 (T_m=99 °C) reveal a strong impact of the nature of the diol repeating unit on degradation rates, possibly related to the density of ester groups in the amorphous phase. Depolymerization by methanolysis indicates suitability for closed-loop recycling.     

Observing the Entry Events of a Titanium-Based Photoredox Catalytic Cycle in Real Time

Titanium-based catalysis in single electron transfer (SET) steps has evolved into a versatile approach for the synthesis of fine chemicals and first attempts have recently been made to enhance its sustainability by merging it with photo-redox (PR) catalysis. Here, we explore the photochemical principles of all-Ti-based SET-PR-catalysis, i.e. in the absence of a precious metal PR-co-catalyst. By combining time-resolved emission with ultraviolet-pump/mid-infrared-probe (UV/MIR) spectroscopy on femtosecond-to-microsecond time scales we quantify the dynamics of the critical events of entry into the catalytic cycle; namely, the singlet-triplet interconversion of the do-it-all titanocene(IV) PR-catalyst and its one-electron reduction by a sacrificial amine electron donor. The results highlight the importance of the PR-catalyst's singlet-triplet gap as a design guide for future improvements.     

Non-Random Island Nucleation in the Electrochemical Roughening on Pt(111)

Many chemical surface systems develop ordered nano-islands during repeated reaction and restoration. Platinum is used in electrochemical energy applications, like fuel cells and electrolysers, although it is scarce, expensive, and degrades. During oxidation-reduction cycles, simulating device operation, nucleation and growth of nano-islands occurs that eventually enhances the dissolution. Preventing nucleation would be the most effective solution. However, little is known about the atomic details of the nucleation; a process almost impossible to observe. Here, we analyze the nuclei-distance distribution mapping out the underlying atomic mechanism: a rarely observed, non-random nucleation takes place. Special, preferential nucleation sites that a priori do not exist, develop initially via a precursor and eventually form a semi-ordered Pt-oxide structure. This precursor mechanism seems to be general, possibly explaining also the nano-island formation on other surfaces/reactions.