Two Ag(I)-Containing Supramolecular Coordination Polymers Constructed from the Multidentate N-donor Ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole Based on Hydrogen-Bonding and π–π Interactions: Syntheses,Crystal Structures,Optical Band Gaps and Luminescent Properties

Two Ag(I)-based coordination polymers, namely [Ag₂(3,3′-tmbpt)(o-Hbdc)₂]·H₂O (1) and [Ag₈(3,3′-tmbpt)₄(1,2,4-Hbtc)₄(H₂O)] (2) (3,3′-tmbpt?=?1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, o-H₂bdc?=?1,2-benzenedicarboxylic acid and 1,2,4-H₃btc?=?1,2,4-benzenetricarboxylic acid), have been synthesized. Single-crystal X-ray diffraction analyses, elemental analyses, infrared spectra, powder X-ray diffraction analyses and thermogravimetric analyses have been carried out to characterize the structures of 1 and 2. Compound 1 shows a (3,4)-connected 2D layered structure with a Schläfli symbol of (4²·6)(4²·6³·8). The intermolecular O–H···O hydrogen-bonding interactions extend the 2D layer into a 3D supramolecular architecture. Compound 2 exhibits a (3,3)-connected double-layered structure with a Schläfli symbol of (4·8·10)₂(8²·10)₂. The intermolecular C–H···O hydrogen-bonding interactions link the double-layers to form a 3D supramolecular architecture. Moreover, there are intramolecular and intermolecular π–π interactions in 1 and 2, which stabilize the whole 3D supramolecular architectures. The band gaps of 1 and 2 are 3.19 and 3.09 eV, respectively, indicating the potential of 1 and 2 as semiconductive materials with wide band gaps. Moreover, 1 and 2 emit intense blue-green light, which may be potential photoactive materials.

Graphic Abstract

Two Ag(I)-based 3D supramolecular coordination polymers constructed from a multidentate N-donor ligand and two aromatic polycarboxylate anions via hydrogen-bonding and π–π interactions have been synthesized and characterized. The band gaps and photoluminescent properties of the compounds have been studied.

     

Unexpected formation of dinaphthoaza-17-crown-5 ether containing γ-aminopiperidine subunit

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Dimensional scaling of flame propagation in discrete particulate clouds

The critical dimension necessary for a flame to propagate in suspensions of fuel particles in oxidiser is studied analytically and numerically. Two types of models are considered: First, a continuum model, wherein the individual particulate sources are not resolved and the heat release is assumed spatially uniform, is solved via conventional finite difference techniques. Second, a discrete source model, wherein the heat diffusion from individual sources is modelled via superposition of the Green's function of each source, is employed to examine the influence of the random, discrete nature of the media. Heat transfer to cold, isothermal walls and to a layer of inert gas surrounding the reactive medium are considered as the loss mechanisms. Both cylindrical and rectangular (slab) geometries of the reactive medium are considered, and the flame speed is measured as a function of the diameter and thickness of the domains, respectively. In the continuum model with inert gas confinement, a universal scaling of critical diameter to critical thickness near 2:1 is found. In the discrete source model, as the time scale of heat release of the sources is made small compared to the interparticle diffusion time, the geometric scaling between cylinders and slabs exhibits values greater than 2:1. The ability of the flame in the discrete regime to propagate in thinner slabs than predicted by continuum scaling is attributed to the flame being able to exploit local fluctuations in concentration across the slab to sustain propagation. As the heat release time of the sources is increased, the discrete source model reverts back to results consistent with the continuum model. Implications of these results for experiments are discussed.     

Integral curvature bounds and diameter estimates on Finsler manifolds

In this paper, we study the integrals of the Ricci curvature over metric balls in a Finsler manifold,which can be viewed as an L~q-norm of the Ricci curvature. By bounding such integrals from above, we obtain several Myers type theorems.     

Predicting polycyclic aromatic hydrocarbon formation with an automatically generated mechanism for acetylene pyrolysis

Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of electronic structure data from the literature and new quantum calculations. Pressure‐dependent kinetics for the CH potential energy surface calculated by Zádor et al. were incorporated to ensure accurate pathways for acetylene initiation reactions. After adding these new data into the RMG database, a pressure‐dependent mechanism was generated in a single RMG simulation which captures chemistry from C to C. In general, the RMG‐generated model accurately predicts major species profiles in comparison to plug‐flow reactor data from the literature. The primary shortcoming of the model is that formation of anthracene, phenanthrene, and pyrene are underpredicted, and PAHs beyond pyrene are not captured. Reaction path analysis was performed for the RMG model to identify key pathways. Notable conclusions include the importance of accounting for the acetone impurity in acetylene in accurately predicting formation of odd‐carbon species, the remarkably low contribution of acetylene dimerization to vinylacetylene or diacetylene, and the dominance of the hydrogen abstraction CH addition (HACA) mechanism in the formation pathways to all PAH species in the model. This work demonstrates the improved ability of RMG to model PAH formation, while highlighting the need for more kinetics data for elementary reaction pathways to larger PAHs.     

Preparation of ZSM‐5 Coated on Monolithic Interconnected Macroporous Al2O3 Using Cheap n‐Butylamine as Template

Using cheap n‐butylamine as template, ZSM‐5 zeolites have been successfully synthesized and coated on monolithic interconnected macroporous Al₂O₃ by the secondary growth method. The use of cheap n‐butylamine could significantly reduce the synthesis cost. Hierarchical monolithic ZSM‐5 zeolites were prepared from synthetic mixtures with different H₂O/Na₂O or SiO₂/Al₂O₃ ratio. The synthesized samples were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR) and N₂ adsorption‐desorption. The results show that the hierarchical monolithic zeolites were obtained with cheap n‐butylamine template as template. During the hydrothermal reaction process, the morphology of the micrometer‐sized support was well maintained. The irregular crystals were formed in a wide range of the H₂O/Na₂O or SiO₂/Al₂O₃ ratio of synthetic mixtures and coated on monolithic Al₂O₃. The relative crystallinity of the zeolites was highest at H₂O/Na₂O=250 or SiO₂/Al₂O₃=160. This type of composites exhibited hierarchical porous structures and relatively high specific surface areas.     

Water‐Soluble Molecularly Imprinted Nanoparticles (MINPs) with Tailored,Functionalized, Modifiable Binding Pockets

Construction of receptors with binding sites of specific size, shape, and functional groups is important to both chemistry and biology. Covalent imprinting of a photocleavable template within surface–core doubly cross‐linked micelles yielded carboxylic acid‐containing hydrophobic pockets within the water‐soluble molecularly imprinted nanoparticles. The functionalized binding pockets were characterized by their binding of amine‐ and acid‐functionalized guests under different pH values. The nanoparticles, on average, contained one binding site per particle and displayed highly selective binding among structural analogues. The binding sites could be modified further by covalent chemistry to modulate their binding properties.     

On the Statistical Calibration of Physical Models

We introduce a novel statistical calibration framework for physical models, relying on probabilistic embedding of model discrepancy error within the model. For clarity of illustration, we take the measurement errors out of consideration, calibrating a chemical model of interest with respect to a more detailed model, considered as “truth” for the present purpose. We employ Bayesian statistical methods for such model‐to‐model calibration and demonstrate their capabilities on simple synthetic models, leading to a well‐defined parameter estimation problem that employs approximate Bayesian computation. The method is then demonstrated on two case studies for calibration of kinetic rate parameters for methane air chemistry, where ignition time information from a detailed elementary‐step kinetic model is used to estimate rate coefficients of a simple chemical mechanism. We show that the calibrated model predictions fit the data and that uncertainty in these predictions is consistent in a mean‐square sense with the discrepancy from the detailed model data.     

A Simple Device for the Solute Elution from Thin-Layer Chromatographic Plates to High-Performance Liquid Chromatographic or Mass Spectrometric Instrument

JPC – Journal of Planar Chromatography – Modern TLC -