Liquid-Phase Cyclohexene Oxidation with O2 over Spray-Flame-Synthesized La1−xSrxCoO3 Perovskite Nanoparticles

La_1−xSr_xCoO₃ (x=0, 0.1, 0.2, 0.3, 0.4) nanoparticles were prepared by spray-flame synthesis and applied in the liquid-phase oxidation of cyclohexene with molecular O₂ as oxidant under mild conditions. The catalysts were systematically characterized by state-of-the-art techniques. With increasing Sr content, the concentration of surface oxygen vacancy defects increases, which is beneficial for cyclohexene oxidation, but the surface concentration of less active Co²⁺ was also increased. However, Co²⁺ cations have a superior activity towards peroxide decomposition, which also plays an important role in cyclohexene oxidation. A Sr doping of 20 at. % was found to be the optimum in terms of activity and product selectivity. The catalyst also showed excellent reusability over three catalytic runs; this can be attributed to its highly stable particle size and morphology. Kinetic investigations revealed first-order reaction kinetics for temperatures between 60 and 100 °C and an apparent activation energy of 68 kJ mol⁻¹ for cyclohexene oxidation. Moreover, the reaction was not affected by the applied O₂ pressure in the range from 10 to 20 bar. In situ attenuated total reflection infrared spectroscopy was used to monitor the conversion of cyclohexene and the formation of reaction products including the key intermediate cyclohex-2-ene-1-hydroperoxide; spin trap electron paramagnetic resonance spectroscopy provided strong evidence for a radical reaction pathway by identifying the cyclohexenyl alkoxyl radical.     

Micromachined optical microphone structures with low thermal-mechanical noise levels

Micromachined microphones with diffraction-based optical displacement detection have been introduced previously [Hall et al., J. Acoust. Soc. Am. 118, 3000-3009 (2005)]. The approach has the advantage of providing high displacement detection resolution of the microphone diaphragm independent of device size and capacitance-creating an unconstrained design space for the mechanical structure itself. Micromachined microphone structures with 1.5-mm-diam polysilicon diaphragms and monolithically integrated diffraction grating electrodes are presented in this work with backplate architectures that deviate substantially from traditional perforated plate designs. These structures have been designed for broadband frequency response and low thermal mechanical noise levels. Rigorous experimental characterization indicates a diaphragm displacement detection resolution of 20 fm radicalHz and a thermal mechanical induced diaphragm displacement noise density of 60 fm radicalHz, corresponding to an A-weighted sound pressure level detection limit of 24 dB(A) for these structures. Measured thermal mechanical displacement noise spectra are in excellent agreement with simulations based on system parameters derived from dynamic frequency response characterization measurements, which show a diaphragm resonance limited bandwidth of approximately 20 kHz. These designs are substantial improvements over initial prototypes presented previously. The high performance-to-size ratio achievable with this technology is expected to have an impact on a variety of instrumentation and hearing applications.     

Synthesis,characterization, and crystal structure of 6,7a-dichloro-3a-hydroxyoctahydro-1<Emphasis Type="Italic">H</Emphasis>-indene-2,5-diyl diacetates

The first syntheses and characterizations of 6,7a-dichloro-3a-hydroxyoctahydro-1H-indene-2,5-diyl diacetates were successfully obtained starting from indan-2-ol. Epoxidation of 2 was carried out using mCPBA in methylene chloride followed by acetylation using acetyl chloride to furnish the diacetates. The structures of all synthesized compounds were characterized by spectroscopic methods.     

Diels–Alder Reactions of Novel (1′‐Arylallylidene)cyclopropanes with Heterodienophiles

Palladium‐catalyzed cross‐coupling of various aryl iodides with bicyclopropylidene provided isolable (1′‐arylallylidene)cyclopropanes, which reacted with a number of carbonyl compounds in the presence of Eu(fod)₃ under high pressure to furnish oxaspiro[2.5]octene derivatives in moderate to good yields (22–69 %). The reactions of the allylidenecyclopropanes with two azo compounds as dienophiles afforded diazaspiro[2.5]octenes in high yields (82 and 99 %) even at ambient pressure. When treated with nitrosobenzene, two of the allylidenecyclopropanes gave the Diels–Alder adducts in up to 83 and 40 % yield. 2,5‐Diiodo‐p‐xylene coupled twice with bicyclopropylidene, and the product underwent a twofold Diels–Alder reaction with nitrosobenzene to produce the bis(spirocyclopropaneoxazine) derivative in 88 % yield. This overall transformation can be brought about in a one‐pot, two‐step operation by addition of the nitrosoarene to the reaction mixture immediately after formation of the allylidenecyclopropanes to furnish various 5‐oxa‐4‐azaspiro[2.5]oct‐7‐ene derivatives in 22–77 % yield. The coupling of methyl bicyclopropylidenecarboxylate with 2,6‐dimethylphenyl iodide produced a mixture of very stable regioisomeric allylidenecyclopropane derivatives in 90 % yield. The reaction of this mixture with N‐phenyltriazolinedione gave a corresponding mixture of the spirocyclopropanated heterobicycles in 61 % yield.     

Epithelial-to-Mesenchymal Transition Is Not a Major Modulating Factor in the Cytotoxic Response to Natural Products in Cancer Cell Lines

Numerous natural products exhibit antiproliferative activity against cancer cells by modulating various biological pathways. In this study, we investigated the potential use of eight natural compounds (apigenin, curcumin, epigallocatechin gallate, fisetin, forskolin, procyanidin B2, resveratrol, urolithin A) and two repurposed agents (fulvestrant and metformin) as chemotherapy enhancers and mesenchymal-to-epithelial (MET) inducers of cancer cells. Screening of these compounds in various colon, breast, and pancreatic cancer cell lines revealed anti-cancer activity for all compounds, with curcumin being the most effective among these in all cell lines. Although some of the natural products were able to induce MET in some cancer cell lines, the MET induction was not related to increased synergy with either 5-FU, irinotecan, gemcitabine, or gefitinib. When synergy was observed, for example with curcumin and irinotecan, this was unrelated to MET induction, as assessed by changes in E-cadherin and vimentin expression. Our results show that MET induction is compound and cell line specific, and that MET is not necessarily related to enhanced chemosensitivity.     

Minimal Surfaces in Hyperbolic 3‐Manifolds

We show the existence of smoothly embedded closed minimal surfaces in infinite volume hyperbolic 3 ‐manifolds except for some special cases. © 2020Wiley Periodicals LLC     

Carbon nitride-coated transparent glass vials as photoinitiators for radical polymerization

Benign polymerization routes offer new perspectives in current polymer technology. Especially for automated or continuous flow synthesis of polymers, new devices and principles have to be considered by the means of minimizing addition or separation sequences as well as the type of a polymer initiation. Near-UV and visible light-induced polymerization utilizing metal-free semiconductor polymeric carbon nitride (pCN) as heterogeneous photocatalyst was a first step into this direction. Moving from heterogeneous powder catalysis (which still requests catalyst separation) to surface photocatalysis via coating glass tubes or vials with pCN thin films is presented. Performance and effectivity of those photoactive reactors are proven by free radical photopolymerization of variety of monomers. Reusability of vials is demonstrated via reversible addition-fragmentation chain-transfer polymerization-assisted block copolymer synthesis. This strategy eliminates the necessity of adding or removing initiators, works at room temperature, and offers a platform for cheap and effective polymer synthesis at the age of automated synthesis.     

Magnetic and magnetocaloric results of magnetic field-induced transitions in La1−xCexMn2Si2 (x=0.35 and 0.45) compounds

The La_1−xCe_xMn₂Si₂ compounds (x=0.35 and 0.45) exhibit an antiferromagnetic-ferromagnetic transition caused by the changes in distance between Mn atoms due to temperature changes. A field-induced transition from antiferromagnetic state to ferromagnetic state at a critical field, which decreases with increase in temperature, can also be induced by applying a magnetic field. In this paper our aim is to study the magnetization and magnetocaloric effect, close to transition temperatures. Our subsidiary aim is to examine the temperature dependence of critical field and ferromagnetic fraction of compounds. The variation of magnetocaloric effect with temperature is correlated with the ferromagnetic-antiferromagnetic phase coexistence. Our final aim is to examine the harmony between magnetocaloric effect values calculated both by the Maxwell theory and by the Landau theory.     

On the way towards a generalized entropy maximization procedure

We propose a generalized entropy maximization procedure, which takes into account the generalized averaging procedures and information gain definitions underlying the generalized entropies. This novel generalized procedure is then applied to Rényi and Tsallis entropies. The generalized entropy maximization procedure for Rényi entropies results in the exponential stationary distribution asymptotically for q∈(0,1] in contrast to the stationary distribution of the inverse power law obtained through the ordinary entropy maximization procedure. Another result of the generalized entropy maximization procedure is that one can naturally obtain all the possible stationary distributions associated with the Tsallis entropies by employing either ordinary or q-generalized Fourier transforms in the averaging procedure.