X-ray absorption signatures of hydrogen-bond structure in water–alcohol solutions

Despite fundamental importance, the experimental characterization of the hydrogen bond network, particularly in multicomponent protic solutions, remains a challenge. Although recent work has experimentally validated that the oxygen K-edge X-ray absorption spectra is sensitive to local hydrogen bond patterns in pure water and aqueous alcohol solutions, the generality of this observation is unknown—as is the sensitivity to the electronic structure of the alcohol cosolvent. In this work, we investigate the electronic structure of water solvated alcohol model geometries using energy specific time-dependent density functional theory to calculate oxygen K-edge X-ray excitations. We find that the geometry of dangling hydrogen bonds in pure water is the main contributor to the pre-edge feature seen in the X-ray absorption spectra, agreeing with previous experimental and theoretical work. We then extend this result to solvated alcohol systems and observe a similar phenomenon, yet importantly, the increase of electron donation from alkyl chains to the alcohol OH group directly correlates to the strength of the core excitation on the dangling hydrogen bond model geometry. This trend arises from a stronger transition dipole moment due to electron localization on the OH group.     

NIFTy 3 – Numerical Information Field Theory: A Python Framework for Multicomponent Signal Inference on HPC Clusters

NIFTy , “Numerical Information Field Theory,” is a software framework designed to ease the development and implementation of field inference algorithms. Field equations are formulated independently of the underlying spatial geometry allowing the user to focus on the algorithmic design. Under the hood, NIFTy ensures that the discretization of the implemented equations is consistent. This enables the user to prototype an algorithm rapidly in 1D and then apply it to high‐dimensional real‐world problems. This paper introduces NIFTy  3, a major upgrade to the original NIFTy  framework. NIFTy  3 allows the user to run inference algorithms on massively parallel high performance computing clusters without changing the implementation of the field equations. It supports n‐dimensional Cartesian spaces, spherical spaces, power spaces, and product spaces as well as transforms to their harmonic counterparts. Furthermore, NIFTy  3 is able to handle non‐scalar fields, such as vector or tensor fields. The functionality and performance of the software package is demonstrated with example code, which implements a mock inference inspired by a real‐world algorithm from the realm of information field theory. NIFTy  3 is open‐source software available under the GNU General Public License v3 (GPL‐3) at https://gitlab.mpcdf.mpg.de/ift/NIFTy/tree/NIFTy_3 .     

NOON State Generation with Phonons in Acoustic Wave Resonators Assisted by a Nitrogen‐Vacancy‐Center Ensemble

Since the quality factor of an acoustic wave resonator (AWR) reached 10¹¹, AWRs have been regarded as a good carrier of quantum information. In this paper, a scheme to construct a NOON state with two AWRs assisted by a nitrogen‐vacancy‐center ensemble (NVE) is proposed. The two AWRs cross each other vertically, and the NVE is located at the center of the crossing. By considering the decoherence of the system and using resonant interactions between the AWRs and the NVE, and the single‐qubit operation of the NVE, a NOON state can be achieved with a fidelity higher than 98.8% when the number of phonons in the AWR is $N\le 3$.     

DNA interaction,cytotoxicity and molecular structure of cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide in the presence of secondary ligand pyridine

Novel cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide (sulfachloropyridazine) has been synthesized and characterized by elemental analysis, FT‐IR spectroscopy and magnetic susceptibility (VSM). Cobalt complex of Sulfachloropyridazine (Co‐SCP) crystallized in monoclinic space group P2₁/n with Z = 4. The structure is solved by direct method and refined to R = 0.099 for 4720 reflections with I ?4σ(I). The results of FT‐IR spectra suggest the binding of cobalt atom to the sulfonamide ligand which is in agreement with the crystal structure determination. In crystal structure, molecule is linked via, C‐H … π, C‐Cl … π and π … π intermolecular interactions. The computational studies like the optimization energy and root means square deviation compare with single crystal structure, frontier molecular orbital (Homo‐Lumo energy) and binding energy of the Co‐SCP has been carried out using DFT/B3LYP level of theory in gaseous phase. Hirshfeld surfaces and the 2D‐fingerprint analysis are performed to study the nature of interactions and their measurable contributions towards crystal packing. The interaction of the complex with DNA is investigated using viscosity measurement and absorption titration studies. The result shows the complex bind to DNA with intercalative mode with high DNA‐binding constant (K_b). Also, in vivo and in vitro cytotoxic studies are performed using S. pombe cells and brine shrimp lethality bioassay. DNA‐cleavage study shows better cleaving ability of the complex.     

Density functional calculations for Rh(I)‐catalyzed C–C bond activation of siloxyvinylcyclopropanes and diazoesters

Density functional theory was employed to investigate rhodium(I)‐catalyzed C–C bond activation of siloxyvinylcyclopropanes and diazoesters. The B3LYP/6‐31G(d,p) level (LANL2DZ(f) for Rh) was used to optimize completely all intermediates and transition states. The computational results revealed that the most favorable pathway was the channel forming the methyl‐branched acyclic product p1 in path A (cyclooctadiene (cod) as the ligand), and the oxidative addition was the rate‐determining step for this channel. It proceeded mainly through the complexation of diazoester to rhodium, rhodium–carbene formation, coordination of siloxyvinylcyclopropane, oxidative addition (C2–C3 bond cleavage) of siloxyvinylcyclopropane, carbene migratory insertion, β‐hydrogen elimination and reductive elimination. The complexation of diazoester to rhodium occurred prior to the coordination of siloxyvinylcyclopropane. Also, the role of the ligands cod, chlorine and 1,4‐dioxane, the effect of di‐rhodium catalyst and the solvent effect are discussed in detail.     

Direct through anionic,cationic, and radical active species: Terminal carbon–halogen bond for “controlled”/living polymerizations of styrene

In this work, we examined the synthesis of novel block (co)polymers by mechanistic transformation through anionic, cationic, and radical living polymerizations using terminal carbon–halogen bond as the dormant species. First, the direct halogenation of growing species in the living anionic polymerization of styrene was examined with CCl₄ to form a carbon–halogen terminal, which can be employed as the dormant species for either living cationic or radical polymerization. The mechanistic transformation was then performed from living anionic polymerization into living cationic or radical polymerization using the obtained polymers as the macroinitiator with the SnCl₄/n‐Bu₄NCl or RuCp^*Cl(PPh₃)/Et₃N initiating system, respectively. Finally, the combination of all the polymerizations allowed the synthesis block copolymers including unprecedented gradient block copolymers composed of styrene and p‐methylstyrene. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 465–473     

Automorphism groups of designs with λ=1

If $G$ is a finite group and $k=q>2$ or $k=q+1$ for a prime power $q$ then, for infinitely many integers $v$, there is a 2-$(v,k,1)$-design $\mathbf{D}$ for which $\mathrm{Aut}\mathbf{D}?G$.     

In vitro anticomplementary activity and quality evaluation of dried blossoms of Inula nervosa Wall. from different geographical origins

Blossoms of Inula nervosa Wall. (BINW) are traditionally used as an analgesic and antitussive in China. In this study, in vitro anticomplementary activities of crude extract from BINW in 21 batches and of extracts of four monomeric compounds were evaluated by the classical pathway. The effect of the region of origin on the quality of BINW was evaluated by fingerprint analysis for the first time. Furthermore, chemometric methods including similarity analysis and principal component analysis were employed to evaluate the quality of BINW. The nine major monomeric compounds were quantitated by ultra‐high‐performance liquid chromatography. All nine analytes demonstrated excellent linearity with recoveries ranging from 97.25% to 102.76%. The limits of detection and quantification were 0.07–12.20 μg/mL and 0.22–40.27 μg/mL, respectively. Results indicate that different regions of origin have a significant effect on the quality of BINW. Fingerprint analysis in combination with chemometrics and multi‐ingredient determination is an efficient and reliable approach for quality evaluation. The BINW samples from Yunnan had the highest ratio of 1,5‐dicaffeoylquinic acid and thymol; they also exhibited significantly higher anticomplementary activity than those from three other areas. This study successfully established a rapid and efficient method to evaluate the quality and biological activity of BINW.