Entanglement of n-heptane and iso-butanol chemistries in flames fueled by their mixtures

This paper concerns itself with the entanglement of the high-temperature oxidation chemistry of n-heptane and iso-butanol in flames fueled by their mixtures. While in many cases the chemistries of the individual fuel components do not interact in mixture flames, in this work, we revealed interactions between the individual species pools originating from n-heptane and iso-butanol oxidation. In a coordinated experimental and modeling effort, chemical structures of three low-pressure premixed flames fueled by different blends of n-heptane and iso-butanol were determined using flame-sampling molecular-beam mass spectrometry with synchrotron-based single-photon ionization and chemical kinetic modeling. The chemical kinetic model, which is based on the reaction set that was used previously [Braun-Unkhoff et al., Proc. Combust. Inst., 2017, 36, 1311–1319], was now extended by an n-heptane sub-mechanism. The overall good performance of the model allows for an extraction of chemically relevant information that highlights the entanglement between the individual fuel-specific species pools. For example, it was shown that methyl radicals, in part from iso-butanol oxidation (i.e., from the decomposition of α-iso-butanol radicals) can participate in n-heptane consumption processes through H-abstraction reactions. Further interactions are related to the formation of the methylallyl radical and aromatics formation. The relevance of such interactions is also discussed regarding the formation of oxygenated byproducts.     

On the role of leptonic CPV phases in cLFV observables

The European Physical Journal C - We argue that high-quality data on the reaction $$e^+e^-\rightarrow \pi ^+\pi ^-\eta $$ will allow one to determine the doubly-virtual form factor $$\eta...     

Tris[2‐(1,3‐thiazol‐2‐yl‐κN)‐1H‐benzimidazole‐κN3]zinc(II) dinitrate ethanol hemisolvate monohydrate at 100 K

The Zn^II center in the dicationic complex of the title compound, [Zn(C₁₀H₇N₃S)₃](NO₃)₂·0.5C₂H₅OH·H₂O, is in a distorted octahedral environment with imperfect noncrystallographic C₃ symmetry. Each 2‐(1,3‐thiazol‐2‐yl)‐1H‐benzimidazole ligand coordinates in a bidentate manner, with the Zn—N(imidazole) bond lengths approximately 0.14 Å shorter than the Zn—N(thiazole) bond lengths. Charge‐assisted hydrogen bonds connect cations, anions and water molecules. A lattice void is occupied by an ethanol solvent molecule disordered about a crystallographic inversion center and π‐stacking is observed between one type of symmetry‐related benzene rings.     

Population and coherence dynamics in large conjugated porphyrin nanorings

In photosynthesis, nature exploits the distinctive electronic properties of chromophores arranged in supramolecular rings for efficient light harvesting. Among synthetic supramolecular cyclic structures, porphyrin nanorings have attracted considerable attention as they have a resemblance to naturally occurring light-harvesting structures but offer the ability to control ring size and the level of disorder. Here, broadband femtosecond transient absorption spectroscopy, with pump pulses in resonance with either the high or the low energy sides of the inhomogeneously broadened absorption spectrum, is used to study the population dynamics and ground and excited state vibrational coherence in large porphyrin nanorings. A series of fully conjugated, alkyne bridged, nanorings constituted of between ten and forty porphyrin units is studied. Pump-wavelength dependent fast spectral evolution is found. A fast rise or decay of the stimulated emission is found when large porphyrin nanorings are excited on, respectively, the high or low energy side of the absorption spectrum. Such dynamics are consistent with the hypothesis of a variation in transition dipole moment across the inhomogeneously broadened ground state ensemble. The observed dynamics indicate the interplay of nanoring conformation and oscillator strength. Oscillatory dynamics on the sub-ps time domain are observed in both pumping conditions. A combined analysis of the excitation wavelength-dependent transient spectra along with the amplitude and phase evolution of the oscillations allows assignment to vibrational wavepackets evolving on either ground or excited states electronic potential energy surfaces. Even though porphyrin nanorings support highly delocalized electronic wavefunctions, with coherence length spanning tens of chromophores, the measured vibrational coherences remain localised on the monomers. The main contributions to the beatings are assigned to two vibrational modes localised on the porphyrin cores: a Zn–N stretching mode and a skeletal methinic/pyrrolic C–C stretching and in-plane bending mode.

Pump wavelength-dependent, ultrafast excited state dynamics arising from inhomogeneous broadening and ground and excited state nuclear wavepackets were observed for a series of Zn porphyrin nanorings made of 10 to 40 repeating units.     

Subcomponent self-assembly of circular helical Dy6(L)6 and bipyramid Dy12(L)8 architectures directed via second-order template effects

In situ metal-templated (hydrazone) condensation also called subcomponent self-assembly of 4,6-dihydrazino-pyrimidine, o-vanillin and dysprosium ions resulted in the formation of discrete hexa- or dodecanuclear metallosupramolecular Dy₆(L)₆ or Dy₁₂(L)₈ aggregates resulting from second-order template effects of the base and the lanthanide counterions used in these processes. XRD analysis revealed unique circular helical or tetragonal bipyramid architectures in which the bis(hydrazone) ligand L adopts different conformations and shows remarkable differences in its mode of metal coordination. While a molecule of trimethylamine acts as a secondary template that fills the void of the Dy₆(L)₆ assembly, sodium ions take on this role for the formation of heterobimetallic Dy₁₂(L)₈ by occupying vacant coordination sites, thus demonstrating that these processes can be steered in different directions upon subtle changes of reaction conditions. Furthermore, Dy₆(L)₆ shows an interesting spin-relaxation energy barrier of 435 K, which is amongst the largest values within multinuclear lanthanide single-molecular magnets.

Subcomponent self-assembly gave access to Dy₁₂(L)₈ and Dy₆(L)₆ architectures via second-order template effects. The Dy₆(L)₆ assembly behaves as a single-molecule magnet exhibiting a high anisotropy barrier and butterfly-shaped magnetic hysteresis.     

How to Secure Valid Quantizations

Canonical quantization has created many valid quantizations that require infinite-line coordinate variables. However, the half-harmonic oscillator, which is limited to the positive coordinate half, cannot receive a valid canonical quantization because of the reduced coordinate space. Instead, affine quantization, which is a new quantization procedure, has been deliberately designed to handle the quantization of problems with reduced coordinate spaces. Following examples of what affine quantization is, and what it can offer, a remarkably straightforward quantization of Einstein’s gravity is attained, in which a proper treatment of the positive definite metric field of gravity has been secured.     

Trusted Threat Intelligence Sharing in Practice and Performance Benchmarking through the Hyperledger Fabric Platform

Historically, threat information sharing has relied on manual modelling and centralised network systems, which can be inefficient, insecure, and prone to errors. Alternatively, private blockchains are now widely used to address these issues and improve overall organisational security. An organisation’s vulnerabilities to attacks might change over time. It is utterly important to find a balance among a current threat, the potential countermeasures, their consequences and costs, and the estimation of the overall risk that this provides to the organisation. For enhancing organisational security and automation, applying threat intelligence technology is critical for detecting, classifying, analysing, and sharing new cyberattack tactics. Trusted partner organisations can then share newly identified threats to improve their defensive capabilities against unknown attacks. On this basis, organisations can help reduce the risk of a cyberattack by providing access to past and current cybersecurity events through blockchain smart contracts and the Interplanetary File System (IPFS). The suggested combination of technologies can make organisational systems more reliable and secure, improving system automation and data quality. This paper outlines a privacy-preserving mechanism for threat information sharing in a trusted way. It proposes a reliable and secure architecture for data automation, quality, and traceability based on the Hyperledger Fabric private-permissioned distributed ledger technology and the MITRE ATT&CK threat intelligence framework. This methodology can also be applied to combat intellectual property theft and industrial espionage.     

Distribution of Platinum and Palladium between Dissolved,Nanoparticulate, and Microparticulate Fractions of Road Dust

Ageing processes of vehicle catalytic converters inevitably lead to the release of Pt and Pd into the environment, road dust being the main sink. Though Pt and Pd are contained in catalytic converters in nanoparticulate metallic form, under environmental conditions, they can be transformed into toxic dissolved species. In the present work, the distribution of Pt and Pd between dissolved, nanoparticulate, and microparticulate fractions of Moscow road dust is assessed. The total concentrations of Pt and Pd in dust vary in the ranges 9–142 ng (mean 35) and 155–456 (mean 235) ng g⁻¹, respectively. The nanoparticulate and dissolved species of Pt and Pd in dust were studied using single particle inductively coupled plasma mass spectrometry. The median sizes of nanoparticulate Pt and Pd were 7 and 13 nm, respectively. The nanoparticulate fraction of Pt and Pd in Moscow dust is only about 1.6–1.8%. The average contents of dissolved fraction of Pt and Pd are 10.4% and 4.1%, respectively. The major fractions of Pt and Pd (88–94%) in road dust are associated with microparticles. Although the microparticulate fractions of Pt and Pd are relatively stable, they may become dissolved under changing environmental conditions and, hence, transformed into toxic species.     

Kribbellichelins A and B,Two New Antibiotics from Kribbella sp. CA-293567 with Activity against Several Human Pathogens

Current needs in finding new antibiotics against emerging multidrug-resistant superbugs are pushing the scientific community into coming back to Nature for the discovery of novel active structures. Recently, a survey of halophilic actinomyectes from saline substrates of El Saladar del Margen, in the Cúllar-Baza depression (Granada, Spain), led us to the isolation and identification of 108 strains from the rhizosphere of the endemic plant Limonium majus. Evaluation of the potential of these strains to produce new anti-infective agents against superbug pathogens was performed through fermentation in 10 different culture media using an OSMAC approach and assessment of the antibacterial and antifungal properties of their acetone extracts. The study allowed the isolation of two novel antibiotic compounds, kribbellichelin A (1) and B (2), along with the known metabolites sandramycin (3), coproporphyrin III (4), and kribelloside C (5) from a bioassay-guided fractionation of scaled-up active extracts of the Kribbella sp. CA-293567 strain. The structures of the new molecules were elucidated by ESI-qTOF-MS/MS, 1D and 2D NMR, and Marfey’s analysis for the determination of the absolute configuration of their amino acid residues. Compounds 1–3 and 5 were assayed against a panel of relevant antibiotic-resistant pathogenic strains and evaluated for cytotoxicity versus the human hepatoma cell line HepG2 (ATCC HB-8065). Kribbellichelins A (1) and B (2) showed antimicrobial activity versus Candida albicans ATCC-64124, weak potency against Acinetobacter baumannii MB-5973 and Pseudomonas aeruginosa MB-5919, and an atypical dose-dependent concentration profile against Aspergillus fumigatus ATCC-46645. Sandramycin (3) confirmed previously reported excellent growth inhibition activity against MRSA MB-5393 but also presented clear antifungal activity against C. albicans ATCC-64124 and A. fumigatus ATCC-46645 associated with lower cytotoxicity observed in HepG2, whereas Kribelloside C (5) displayed high antifungal activity only against A. fumigatus ATCC-46645. Herein, we describe the processes followed for the isolation, structure elucidation, and potency evaluation of these two new active compounds against a panel of human pathogens as well as, for the first time, the characterization of the antifungal activities of sandramycin (3).