Effect of Acid Treatment of Montmorillonite on “Support‐Activator” Performance to Support Metallocene for Propylene Polymerization Catalyst

This work is focused on montmorillonite (MMT)‐based “support‐activators” (S‐As) for the metallocene‐catalyzed propylene polymerization. This catalyst was previously industrialized; however, for further technological advances, the activation mechanism is investigated. The chemical and morphological requirements of the S‐A are surveyed using both commercially available raw clay minerals (non‐acid‐treated) and acid‐treated clay minerals. The S‐A possessing strong‐acid sites (pK a < ?8.2) gives a highly active catalyst. Acid treatment of MMT induces morphological changes as well as the formation of strong acid sites. Based on pore size distribution analysis and atomic force microscopy observations, it is concluded that the strong acid sites are located in the small pores around the edge of the clay mineral (not in the interlayer), where the structure is disordered by the acid treatment.

     

A non-negative matrix factorization model based on the zero-inflated Tweedie distribution

Non-negative matrix factorization (NMF) is a technique of multivariate analysis used to approximate a given matrix containing non-negative data using two non-negative factor matrices that has been applied to a number of fields. However, when a matrix containing non-negative data has many zeroes, NMF encounters an approximation difficulty. This zero-inflated situation occurs often when a data matrix is given as count data, and becomes more challenging with matrices of increasing size. To solve this problem, we propose a new NMF model for zero-inflated non-negative matrices. Our model is based on the zero-inflated Tweedie distribution. The Tweedie distribution is a generalization of the normal, the Poisson, and the gamma distributions, and differs from each of the other distributions in the degree of robustness of its estimated parameters. In this paper, we show through numerical examples that the proposed model is superior to the basic NMF model in terms of approximation of zero-inflated data. Furthermore, we show the differences between the estimated basis vectors found using the basic and the proposed NMF models for \(\beta \) divergence by applying it to real purchasing data.     

Cover Feature: Fluoroalkyl Sulfoximines for Versatile Photocatalytic Radical Fluoroalkylations (Chem. Rec. 9/2023)

Fluoroalkyl sulfoximines, which serve as electron-accepting fluoroalkyl radical sources, are easy-to-handle, solid, and bench-stable chemicals. Fluoroalkyl radicals can be generated from sulfoximine reagents using strong one-electron injectors, such as a highly reducing photoredox catalyst in the excited state. Our group has developed photocatalytic radical di- and mono-fluoromethylation and α-monofluoroalkylation of olefins with the corresponding fluoroalkyl sulfoximines. In this personal account, appropriate combinations of fluoroalkyl sulfoximines and photoredox catalysts, leading to successful radical fluoroalkylation, have been discussed.     

Microinjection Molded Biopolymeric Airway Stent with Antibacterial and Anti-Hyperplastic Properties

Central airway stenosis is a condition that the diameter of the trachea or main bronchus shrinkage is caused by external compression or internal tissue hyperplasia, which can cause difficulty breathing, asphyxia, and even death. Airway stenting is an easy way to restore the patency of the central airway, but airway stents commonly used in clinical practice can lead to complications such as mucus plugging, bacterial infection, and granulation tissue hyperplasia. Moreover, the non-degradable characteristic makes it requires a second operation to remove, which has the potential to cause tissue damage. In this study, a biodegradable airway stent is fabricated by microinjection molding using the bioelastomer of poly (L-lactide-co-ε-caprolactone) as the matrix material. The airway stent has excellent mechanical properties and an appropriate degradation rate. The hydrophilic surface of the airway stent can inhibit mucus plugging. The loading of silver nanoparticles and cisplatin endows the stent with antibacterial and anti-hyperplastic functions. In vitro and in vivo experiments demonstrate that this study provides an antibacterial and anti-hyperplastic biodegradable airway stent with elastic properties to avoid secondary removal operation and reduce complications associated with mucus plugging, bacterial infection, and granulation tissue hyperplasia.     

Spectral Mismatch Effect of Ultraviolet Radiometers in Actual UV-C Measurement

The management of radiant exposure to ultraviolet (UV) radiation, especially in the wavelength range from 100 nm to 280 nm (i.e. UV-C), is important for virus inactivation or photobiological safety. Recently, many commercial UV radiometers have been used to measure UV-C irradiance for industrial and public applications. The accuracy of the four types of commercial UV radiometers was investigated by comparing the reference irradiance values obtained from the spectral irradiance standard. It was found that the displayed values of the UV radiometers have discrepancies, such that the measured value can be more than twice the actual value in a certain case. The spectral mismatch between the calibration and test sources is a major factor in the discrepancies in the UV-C measurements. With spectral mismatch correction, most corrected values show a tendency to improve the result to approaching the reference values within 20%. Users need to provide spectral information about the source and radiometer used for UV-C measurement.     

Synthesis of optically inactive cellulose via cationic ring-opening polymerization

Cellulose, which comprises D-glucose and L-glucose (D,L-cellulose), was synthesized from D-glucose (1D) and L-glucose (1L) via cationic ring-opening polymerization. Specifically, the ring-opening copolymerization of 3-O-benzyl-2,6-di-O-pivaloyl-β-D-glucopyranoside (2D) and 3-O-benzyl-2,6-di-O-pivaloyl-β-D-glucopyranoside (2L), synthesized from compounds 1D and 1L, respectively, in a 1:1 ratio, afforded 3-O-benzyl-2,6-di-O-β-D,L-glucopyranan (3DL) with a degree of polymerization (DPn) of 28.5 (Mw/Mn?=?1.90) in quantitative yield. The deprotection of compound 3DL and subsequent acetylation proceeded smoothly to afford acetylated compound 4DL with a DPn of 18.6 (Mw/Mn?=?2.08). The specific rotation of acetylated compound 4DL was?+?0.01°, suggesting that acetylated compound 4DL was optically inactive cellulose triacetate. Furthermore, before acetylation, compound 4DL was an optically inactive cellulose comprising an almost racemic mixture of D-glucose and L-glucose. Compound 4DL was an amorphous polymer. This is the first reported synthesis of optically inactive D,L-cellulose.

     

Hyperpolarized 13C Magnetic Resonance Imaging of Fumarate Metabolism by Parahydrogen-induced Polarization: A Proof-of-Concept in vivo Study

Hyperpolarized [1-¹³C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-¹³C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-¹³C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-¹³C]fumarate at sufficient ¹³C polarization for ex vivo detection of hyperpolarized ¹³C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo ¹³C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis.     

Water revealed as molecular mirror when measuring low concentrations of sugar with near infrared light

Near infrared spectroscopy is an overtone spectroscopy regarded as a quick and non-destructive method that provides analytical solutions for components that represent approximately 1% or more of the total mass of the investigated composite samples. Aquaphotomics offers the possibility for disentanglement of information remaining hidden in the spectra when conventional data evaluation methods are used, since this concept utilizes changes of the water structure induced by the measured solute as specific molecular vibrations at water bands. Here, near infrared technique and aquaphotomics are applied for non-destructive identification and quantification of mono- and di-saccharide solutes at 100–0.02 mM concentration that is accepted as unachievable with near infrared spectroscopy. The results presented in this study support the aquaphotomics' water molecular mirror concept that explores spectral changes related to water molecular rearrangements caused by minute changes of the solutes in the aqueous systems. The method provides quick and accurate alternative for classical analytical measurements of saccharides even at millimolar concentration levels.     

Computational study on the interactions of mustard gas with cucurbituril macrocycles

The study on the absorption of toxic gases such as mustard gas by organic host is essential to the development of inexpensive detection and decontamination equipments. Using quantum chemical methods, we propose cucurbituril as an effective host to capture mustard gas. It was found that stable complexes are formed with the inclusion of the toxic gas molecules inside the cucurbituril cavity, compared with the lateral and exterior interactions. Oxygen mustard has a comparable binding energy with sulfur mustard and hence can be used during experimental investigation. Additionally, during the inclusion complex formation, the presence of heteroatoms helps the guest molecules to undergo a larger structural reorganization to get accommodated inside the cucurbituril macromolecule. Atoms‐in‐molecules analysis shows the existence of strong intermolecular CH…O bonding between the guest molecules and cucurbituril macromolecule. The presence of an intramolecular CH…Cl type of bonding accounts for the higher stabilization of sulfur mustard inside the cucurbituril macromolecule. © 2015 Wiley Periodicals, Inc.     

An Anti CuO2‐type Metal Hydride Square Net Structure in Ln2M2As2Hx (Ln=La or Sm,M=Ti,V, Cr,or Mn)

Using a high pressure technique and the strong donating nature of H⁻, a new series of tetragonal La₂Fe₂Se₂O₃‐type layered mixed‐anion arsenides, Ln₂M₂As₂H_x, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x≈3). In these compounds, an unusual M₂H square net, which has anti CuO₂ square net structures accompanying two As³⁻ ions, is sandwiched by (LaH)₂ fluorite layers. Notably, strong metal–metal bonding with a distance of 2.80 Å was confirmed in La₂Ti₂As₂H_2.3, which has metallic properties. In fact, these compounds are situated near the boundary between salt‐like ionic hydrides and transition‐metal hydrides with metallic characters.