Highly Sensitive Switchable Sensors for Hydroxide on Glass Surfaces Based on Isoquinolinium-Quinolinium-substituted Acetylenes.

Bi-substituted acetylenes with a quinolinium and an isoquinolinium substituent are described, which reversibly form intensely colored adducts with O-nucleophiles and thus enable the detection of >0,5 ppm hydroxide on the surfaces of various glasses. Acids reconstitute the colorless bi-substituted acetylenes. The quinolinium and isoquinolinium rings are bound via their 2-, 3-, 4- and 1-, 3-, 4-positions to the triple bond, respectively. The choice of substitution sites of the hetarenium rings enables the design of mixed conjugated/cross-conjugated π-electron systems. Depending on the combination of binding sites, the frontier orbital profile, the triple bond polarization, the fluorescence behaviour, and the sensitivity to hydroxide differs.

Sydnone Methides-A Forgotten Class of Mesoionic Compounds for the Generation of Anionic N-Heterocyclic Carbenes.

Sydnone methides are described from which only one single example has been mentioned in the literature so far. Their deprotonation gave anions which can be formulated as π-electron rich anionic N-heterocyclic carbenes. Sulfur and selenium adducts were stabilized as their methyl ethers, and mercury, gold as well as rhodium complexes of the sydnone methide carbenes were prepared. Sydnone methide anions also undergo C-C coupling reactions with 1-fluoro-4-iodobenzene under Pd(PPh3 )4 and CuBr catalysis. 77 Se NMR resonance frequencies and 1 JC4-Se as well as 1 JC4-H coupling constants have been determined to gain knowledge about the electronic properties of the anionic N-heterocyclic carbenes. The carbene carbon atom of the sydnone methide anion 3 j resonates at δ=155.2 ppm in 13 C NMR spectroscopy at -40 °C which is extremely shifted upfield in comparison to classical N-heterocyclic carbenes.

Customizing the Appearance of Sparks with Binary Metal Alloys.

Long-flying sparks are an essential part of several pyrotechnic effects. Unfortunately, and in contrast to colored flames, the color space of sparks is basically limited to the black body curve. With low-boiling-point metals, vapor-phase combustion and bright colorful flashes are achievable. Since 1999, alloys of rare-earth elements have been proposed for colorful spark generation. To the best of our knowledge, here, we present the first investigation of such alloys to change the color of sparks beyond the black body limit. Alloys consisting of >65 at. % of a brightly emitting and low-boiling-point metal and a carrier metal allow achieving long-flying deeply colored sparks. Besides the color, branching of sparks is crucial for the visual appearance. Rare-earth metals were found to promote branching of different alloys. Finally, fountains ejecting golden/green sparks based on a stable eutectic Yb-Cu alloy and continuously branching sparks based on Nd2Fe14B are presented.

Formation of Titanium Nitride, Titanium Carbide, and Silicon Carbide Surfaces by High Power Femtosecond Laser Treatment.

Invited for this month's cover is the group of Prof. Eike G. Hübner at Fraunhofer Heinrich Hertz Institute HHI, Goslar and Clausthal University of Technology, Clausthal-Zellerfeld, Germany. The cover picture shows a titanium plate, on which the crystal structure (golden circle=Ti, blue circle=O/N/C) of isomorphous TiO, TiN or TiC, respectively, has been engraved by a high-power high pulse repetition rate femtosecond laser process. The process allows for a fast and spatially resolved surface transformation of titanium to golden TiN, blue TiO/TiO2 or black TiC in an atmosphere of nitrogen, air or ethene/argon. The background represents a typical surface microstructure of these interstitial compounds obtained during this transformation. Read the full text of the article at 10.1002/cplu.202100118.

Formation of Titanium Nitride, Titanium Carbide, and Silicon Carbide Surfaces by High Power Femtosecond Laser Treatment.

Coatings based on titanium nitrides, titanium carbides and silicon carbides can optimize the surface properties of titanium or silicon for various applications ranging from biocompatibility to chemical stability and durability. Here, we investigated a high power (100 W) high pulse repetition rate femtosecond laser process (λ=1030 nm, τ=750 fs, f=1 MHz) for the treatment of titanium and silicon in atmospheres of argon, nitrogen, methane, ethene and acetylene. In a nitrogen atmosphere, a homogeneous coating of TiON is formed on titanium. In an ethene/argon atmosphere coatings of TiOC and SiC are formed on Ti and Si, respectively. The process allows a fast surface transformation with a process rate of 0.33 cm2 s-1 and a high spatial resolution below 0.5 mm with a minimal heat affected zone at the same time. In contrast to low repetition rate femtosecond laser processed samples, the surfaces are more robust against mechanical impact. At the same time, the surfaces reveal a distinct microstructure in comparison to coatings obtained by vapor deposition techniques.

Studies of Langmuir and Langmuir-Schaefer Films of Poly(3-Hexylthiophene) and Poly(Vinylidene Fluoride).

The synergistic use of blends of regioregular poly(3-hexylthiophene) (P3HT) and poly(vinylidene fluoride) (PVDF) or poly((vinylidene fluoride)-block-(methyl methacrylate)) (PVDF-PMMA) to form Langmuir and Langmuir-Schaefer (LS) films is reported. P3HT has wide applications in sensor devices because of its properties such as conductivity, luminescence, and chromism; however, the stiffness of the films and the difficulty in organizing the molecules may pose a problem in these applications. In this context, polymers based on PVDF can be used in the formation of thin P3HT films and present an alternative to improve the organization of P3HT molecules. In addition, PVDF acts as a plasticizer, making the film less rigid. The films were obtained from the blends of P3HT/PVDF and P3HT/PVDF-PMMA in a solution containing chloroform and DMAc (N,N-dimethylacetamide). Surface pressure isotherms, in situ ultraviolet-visible (UV-vis) spectroscopy, polarization-modulation infrared reflection-absorption spectroscopy, and Brewster angle microscopy techniques were used to analyze Langmuir films. The surface morphology of LS films was characterized by atomic force microscopy and UV-vis spectroscopy, and their degradation was analyzed by UV-vis spectroscopy after exposure to natural light under atmospheric conditions. The Langmuir films containing PVDF indicate a direct formation of the ferroelectric ß phase, with dipoles parallel to the water surface. The Langmuir films formed by P3HT presented dipoles of side chains parallel and aromatic groups perpendicular to the water surface. P3HT and PVDF or PVDF-PMMA films show high molecular organization compared with pure P3HT films. The results suggest that these films could be used to improve the properties of P3HT in several device applications, such as in optical and electrical sensors.

Synthesis of γ-hydroxy-α-(arylmethyl)carboxylic acids from lactones: pathway to a structural motif derived from lactic acid and amino acid analogs?

OBJECTIVE: A synthetic pathway to γ-hydroxy-α-(arylmethyl)carboxylic acids starting from α-angelica lactone and γ-butyrolactone was investigated. These γ-hydroxycarboxylic acids resemble structural motifs of lactic acid and amino acids. The possibility of cocondensation with lactic acid towards functionalized poly(lactic acid)s was analyzed. RESULTS: The functional γ-hydroxycarboxylates sodium 4-hydroxy-2-((N-methylpyrazol-4-yl)methyl)pentanoate and sodium 4-hydroxy-2-(phenylmethyl)butanoate (2-benzyl-4-hydroxybutanoate) were synthesized in good yields as a proof of concept for the proposed reaction pathway. Additionally, sodium (E)-2-((N-methylpyrazol-4-yl)methylene)-4-oxopentanoate presenting an interesting structural motif was isolated. All products have been fully characterized by mass spectrometry, IR spectroscopy and 2D nuclear magnetic resonance (NMR) techniques. In contrast to the carboxylate anions, the corresponding carboxylic acids obtained after acidification were found to be unstable. The instability was analyzed by NMR experiments. With the help of diffusion ordered NMR spectroscopy, the cocondensation with lactic acid was elucidated. The reaction products were characterized as oligomers of pure lactic acid, while intramolecular condensation of the γ-hydroxycarboxylic acids prevents cocondensation with lactide.

3D-Printing inside the Glovebox: A Versatile Tool for Inert-Gas Chemistry Combined with Spectroscopy.

3D-Printing with the well-established 'Fused Deposition Modeling' technology was used to print totally gas-tight reaction vessels, combined with printed cuvettes, inside the inert-gas atmosphere of a glovebox. During pauses of the print, the reaction flasks out of acrylonitrile butadiene styrene were filled with various reactants. After the basic test reactions to proof the oxygen tightness and investigations of the influence of printing within an inert-gas atmosphere, scope and limitations of the method are presented by syntheses of new compounds with highly reactive reagents, such as trimethylaluminium, and reaction monitoring via UV/VIS, IR, and NMR spectroscopy. The applicable temperature range, the choice of solvents, the reaction times, and the analytical methods have been investigated in detail. A set of reaction flasks is presented, which allow routine inert-gas syntheses and combined spectroscopy without modifications of the glovebox, the 3D-printer, or the spectrometers. Overall, this demonstrates the potential of 3D-printed reaction cuvettes to become a complementary standard method in inert-gas chemistry.