RESUMEN
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 >0,5â 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.
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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 Seâ 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=155.2â ppm in 13 Câ NMR spectroscopy at -40 °C which is extremely shifted upfield in comparison to classical N-heterocyclic carbenes.
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A conical microstructure is one of the most versatile surface textures obtained by ultrashort laser micromachining. Besides an increased surface area, unique surface properties such as superhydrophilicity, increased absorptivity; and thermal emissivity can be tailored. On metals, usually ultrashort laser pulses in the femtosecond to low picosecond range are used to obtain these surface structures, whereas nanosecond laser pulses favor melting processes. Herein, we report on an investigation of reactive gas atmospheres such as oxygen, steam, and halogens during laser micromachining of aluminum with 6â ns laser pulses. At a reduced pressure of 20â hPa (air) with additional iodine vapor as reactive species, we found a perfectly microconical structured surface to be formed with nanosecond laser pulses. The resulting surface structures were proven to be free of residual halogens. The application of nanosecond instead of femtosecond laser pulses for the surface structuring process allows to apply significantly less complex laser sources.
RESUMEN
Diels-Alder reaction of 2-, 3- and 4-(phenylethynyl)quinolines and tetraphenylcyclopentadienone gave three regioisomeric 2,3,4,5,6-pentaphenyl-1-(quinolin-2-yl, -3-yl, and -4-yl)benzenes. Restricted rotation of the 3-yl and 4-yl substituted derivatives is observed between the central core and the substituents, resulting in propeller-shaped molecules. Likewise, 1,2-diquinolinyl-3,4,5,6-tetraphenylbenzenes with 3-yl,3-yl and 3-yl,4-yl connectivity were prepared. As evidenced by NMR spectroscopy, they form two diasteromers due to their restricted rotation. A cobalt-catalyzed [2 + 2 + 2]-cyclotrimerization of 2-(phenylethynyl)quinoline resulted in the formation of triphenyl-2,4,6- and -3,5,6-tri(quinolin-2-yl)benzenes. The same reaction was applied to 3,3'-ethyne-1,2-diyldiquinoline which formed hexa(quinolin-3-yl)benzene. N-Methylation gave the title compounds. Among those, the hexacationic hexa(N-methylquinolinio-3-yl)benzene is described. Stereochemical aspects are predominantly discussed by means of results of NMR experiments. DFT-calculations on the most stable conformations and the frontier orbital profiles of the hexacation as well as of its neutral precursor have been carried out.
RESUMEN
6-Chloropurine and 2,6-dichloropurine were reacted with N1-substituted imidazoles to give purin-6-yl substituted imidazolium salts, respectively. Deprotonation of the 1-methylimidazolium derivative resulted in the formation of the corresponding stable conjugated mesomeric betaine, whereas the 1-phenyl,- 1-vinyl- and 1-(2-hydroxyethyl) derivatives proved to be unstable. In situ generation of the mesomeric betaines by caesium carbonate in the presence of sulfur and selenium, however, gave the thiones and the selenones of the tautomeric purine-substituted imidazol-2-ylidene, respectively. Its anionic N-heterocyclic carbene was formally trapped by reaction with triethylborane at high temperatures as a cyclic boron adduct which is the first representative of a new heterocyclic ring system. DFT calculations gained insight into the electronic properties of the N-heterocyclic carbenes substituted by π-electron donators. Results of a single crystal X-ray analysis of the boron adduct are presented.
RESUMEN
2-(Imidazolium-1-yl)phenolates are conjugated heterocyclic mesomeric betaines in tautomeric equilibrium with the corresponding N-heterocyclic carbenes (NHCs), 3-(2-hydroxyphenyl)-imidazol-2-ylidenes. The carbene tautomers can be trapped as thiones (X-ray analysis). Moreover, bis(triphenylphosphine)palladium(II) dichloride in THF trapped the carbene tautomer as a palladium complex without participation of the phenolate group (X-ray analysis). The corresponding anionic NHCs, 2-phenolate-substituted imidazol-2-ylidenes, can be trapped by triethylborane or triphenylborane to form 4,4-diethyl- or 4,4-diphenyl-4H-benzo[e]imidazo[2,1-c][1,4,2]oxaza-borininium-4-ides, respectively (two X-ray analyses). These tricyclic systems are the first representatives of a new heterocyclic ring system. The results of DFT calculations concerning the HOMO/LUMO profiles and partial charges are also presented.
RESUMEN
3-Ethynylquinoline was subjected to a Sonogashira-Hagihara reaction with methyl 2-, 3-, and 4-bromobenzoates, respectively, and then N-methylated to give 3-[((methoxycarbonyl)phenyl)ethynyl]-1-methylquinolinium salts (two X-ray analyses). On saponification of the 3- and 4-substituted benzoates, the mesomeric betaines 3- and 4-[(1-methylquinolinium-3-yl)ethynyl]benzoates were formed. By contrast, the 2-benzoate derivative gave either the corresponding (1-oxo-1H-isochromen-3-yl)quinolinium derivative or the mesomeric betaine 2-(1-methylquinolinium-3-yl)-1,3-dioxo-2,3-dihydro-1H-inden-2-ide depending on the reaction conditions. A DFT calculation predicts a transoid conformation of the acetylene bond in the intermediate 2-[(1-methylquinolinium-3-yl)ethynyl]benzoate which is due to a strong hydrogen bond between the carboxylate group and 2H of the quinolinium ring, in addition to a 1,5-interaction between the carboxylate group and the CC triple bond. The bond angles of the transoid CC triple bond were calculated to be 211.6° and -175.1° in vacuo. The corresponding linear triple bond is 50.4 kJ/mol less stable in vacuo according to the calculation, and the N-heterocyclic carbene quinoline-2-ylidene is not formed as a tautomer.
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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.
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The hetereoscorpionate ligands bis(pyrazol-1-yl)acetic acid (Hbpza) and bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza) are reacted with [Sn(OAc)2] or [Sn(acac)2] to yield the corresponding Sn(II) complexes. A single crystal X-ray determination for the in solution monomeric complex [Sn(bpza)2] (1a) revealed a dinuclear molecular structure [Sn2(bpza)4] (1b), with κ3-N,N,O-coordinated bpza ligands at each of the Sn(II) and two bpza ligands µ-bridging between the Sn(II) centres. The molecular structure of [Sn(bdmpza)2] (2) exhibits a homoleptic bisligand complex with both ligands displaced by the free electron pair, which is proven by DFT calculations. Oxidation of complex 2 in an attempt to synthesize a homoleptic Sn(IV) complex leads to the formation of [Sn(bdmpza)F3] (3). In addition, homoleptic bisligand gallium complexes [Ga(bdmpza)2][ClO4] (4) and [Ga(bpza)2][GaCl4] (5) were prepared and characterized by 71Ga NMR and IR spectroscopy as well as by X-ray crystallography.
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The dispersion of aerosols was studied experimentally in several concert halls to evaluate their airborne route and thus the risk of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) spreading. For this, a dummy was used that emits simulated human breath containing aerosols (mean diameter of 0.3 µm) and CO2, with a horizontal exhalation velocity of v = 2.4 m/s, measured 10 cm in front of the mouth. Aerosol and CO2 concentration profiles were mapped using sensors placed around the dummy. No substantial enrichment of aerosols and CO2 was found at adjacent seats, provided that (1) there were floor displacement outlets under each seat enabling a minimum local fresh air vertical flow of vv = 0.05 m/s, (2) the air exchange rate (ACH) was more than 3, and (3) the dummy wore a surgical face mask. Knowledge of dispersion of viral droplets by airborne routes in real environments will help in risk assessment when re-opening concert halls and theatres after a pandemic lockdown.
Asunto(s)
COVID-19/transmisión , SARS-CoV-2 , Aerosoles , Humanos , Maniquíes , MáscarasRESUMEN
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 (100â W) high pulse repetition rate femtosecond laser process (λ=1030â nm, τ=750â fs, f=1â 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 0.33â cm2 s-1 and a high spatial resolution below 0.5â 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.
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Invited for this month's cover is the group of Prof. Eikeâ 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.
RESUMEN
Femtosecond laser micromachining is an important and flexible method to generate precisely targeted surfaces on various materials. On titanium, the laser structuring process strongly depends on the laser parameters. For example, an increasement of the pulse length and repetition rate favors melting processes instead of ablation and microstructuring. We report on an investigation of reactive halogens (iodine, bromine, chlorine) and halocarbons as additives to the laser structuring process of pure titanium and the common alloy Ti-6Al-4V with 0.75 ps laser pulses. The choice of the halogen allows control of whether solely the chemical composition or the surface microstructure should be altered. Bromine was found to be an efficient additive to generate homogeneous microstructures based on micropillars at convenient conditions (air, atmospheric pressure). The resulting surfaces have been characterised by scanning electron microscopy, energy dispersive X-ray spectroscopy, thermal emission infrared photography, reflective UV/Vis spectroscopy and contact angle measurements. The bromine/air processed titanium surfaces revealed superhydrophilicity, strongly increased thermal emissivity and a high absorptivity ("black metal").
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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.
Asunto(s)
Aminoácidos/análisis , Vías Biosintéticas , Ácidos Carboxílicos/química , Ácido Láctico/química , Lactonas/química , Espectroscopía de Resonancia Magnética , Poliésteres/químicaRESUMEN
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.
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Deprotonated sydnones, which can be represented as anionic N-heterocyclic carbenes, were prepared as Li adducts and compared with deprotonated O-ethylsydnones (5-ethoxy-1,2,3-oxadiazol-4-ylidenes) which belong to the class of abnormal NHCs. The Pd complexes of the sydnone anions (X-ray analysis) as well as of the O-ethylsydnone carbenes proved to be efficient catalysts in aryl couplings of thiophenes.