A Mechanistic Perspective on the Mechanochemical Method To Reduce Carbonyl Groups with Stainless Steel and Water

Mechanochemistry through high-speed ball milling has become an increasingly popular method for performing organic transformations. This newfound interest in high-speed ball milling is in part driven by the benefit of performing reactions in the absence of solvent. Mechanochemical reactions are often conducted in stainless-steel vials with stainless-steel balls. Since stainless steel is made of several readily oxidizable metals (Fe, Cr, and Ni), reduction reactions using water as a hydrogen source were explored using a temperature-controlled mixer mill. Mechanistic studies suggest that the reduction proceeds via a single electron transfer (SET) pathway, with iron and nickel being essential components for the reaction.     

Luminescent properties of Yb-doped monoclinic yttrium polyphosphates

Yb³⁺-doped monoclinic yttrium polyphosphate Y(PO₃)₃ powder compounds were synthesized and were characterized by X-ray diffraction, IR absorption spectroscopy and Raman scattering spectroscopy.An attempt to use Yb³⁺ ion as structural probe is carried out to investigate the site occupation. Yb³⁺ emission and fluorescence decay studies were carried out both at low and room temperatures. The interpretation of electronic energy level positions has been done by using the comparison of emission spectra with those of vibronic sideband energy positions from Raman scattering spectroscopy.The spectroscopic results are discussed and correlated with the data of the already known monoclinic structure of Y(PO₃)₃ where four slightly different octahedral sites are available for the trivalent rare earth ion.     

Catalytic Properties of Caseinolytic Protease Subunit of Plasmodium knowlesi and Its Inhibition by a Member of δ-Lactone,Hyptolide

The caseinolytic protease (Clp) system plays an essential role in the protein homeostasis of the malaria parasite, particularly at the stage of apicoplast development. The inhibition of this protein is known to have a lethal effect on the parasite and is therefore considered an interesting avenue for antimalaria drugs discovery. The catalytic activity of the Clp system is modulated by its proteolytic subunit (ClpP), which belongs to the serine protease family member and is therefore extensively studied for further inhibitors development. Among many inhibitors, the group of β-lactone is known to be a specific inhibitor for ClpP. Nevertheless, other groups of lactones have never been studied. This study aims to characterize the catalytic properties of ClpP of Plasmodium knowlesi (Pk-ClpP) and the inhibition properties of a δ-lactone hyptolide against this protein. Accordingly, a codon-optimized synthetic gene encoding Pk-ClpP was expressed in Escherichia coli BL21(DE3) and purified under a single step of Ni²⁺-affinity chromatography, yielding a 2.20 mg from 1 L culture. Meanwhile, size-exclusion chromatography indicated that Pk-ClpP migrated primarily as homoheptameric with a size of 205 kDa. The specific activity of pure Pk-ClpP was 0.73 U µg⁻¹, with a catalytic efficiency k_cat/K_M of 0.05 µM⁻¹ s⁻¹, with optimum temperature and pH of 50 °C and 7.0–7.5, respectively. Interestingly, hyptolide, a member of δ-lactone, was shown to inhibit Pk-ClpP with an IC₅₀ value of 17.36 ± 1.44 nM. Structural homology modelling, secondary structure prediction, and far-UV CD spectra revealed that helical structures dominate this protein. In addition, the structural homology modeling showed that this protein forms a barrel-shaped homoheptamer. Docking simulation revealed that the inhibition was found to be a competitive inhibition in which hyptolide was able to dock into the catalytic site and block the substrate. The competitiveness of hyptolide is due to the higher binding affinity of this molecule than the substrate.     

4‐Acetonyl­idene‐1‐ethyl‐2,3,4,5‐tetra­hydro‐1H‐1,5‐benzodiazepin‐2‐one

The title compound, C₁₄H₁₆N₂O₂, contains a diazepine ring, which appears in a boat conformation. An intramolecular hydrogen bond is formed between the NH group of the diazepine ring and a carbonyl O atom of one of the side chains.     

DWDM混合光学系统中帧间和信道内四波混频效应的抑制

本文提出了光码多分址（CDMA）和光密集波分复用（DWDM）的混合系统,全面研究了四波混频（FWM）的影响。在这个系统中,主要存在两个四波混频问题：包括多址干扰（MAI）和码间干扰（ISI）的帧间四波混频和信道内四波混频。结果表明,综合考虑信道间和信道内四波混频的影响,最佳发射功率可选为18 dBm。当发射功率大于18 dBm时,混合系统的误码率（BER）将增加。基于此,本文提出了一种电光相位调制器（EOPM）模块,将其放置在波分复用器之后,通过抑制信道内四波混频的影响,同时调制所有波长信号的相位,从而增加混合系统的非线性容限,这极大地改善了基于OOK传输的光学CDMA-DWDM混合系统的性能。此外,由于多对角线（MD）结构具有零互相关特性,通过使用多对角线识别序列码可以减少多址干扰的影响。结果还表明,CDMA技术与色散相结合有助于降低信道间四波混频的影响。此外,识别序列码间隔在减轻码间干扰中起着至关重要的作用,如结果所示,当识别序列码间隔压缩至比特持续时间的25%时,可以避免码间干扰,此时所提出的混合系统的性能最佳。     

哒嗪与苯、庚氧基取代苯共聚物的合成

1,3-双(二苯基瞵)-丙烷基-二氯化镍存在下,3,6-二氯哒嗪与1,4-二溴苯格氏试剂共聚,庚氧基取代苯与3,6-二氯哒嗪格氏试剂共聚得到了哒嗪类新型共轭共聚物。并用FTIR、NMR对中间体和聚合物的结构进行了表征。采用XRD测试对共聚物结晶性进行了讨论。该合成方法所得的共聚物收率分别为75％和67％。其中含有烷氧基苯单元的共聚物在DMF、DMSO等极性溶剂和有机酸中具有良好的溶解性。共聚物的紫外-可见光谱中,分别在310nm、345nm等处出现最大吸收峰。XRD结果表示共聚物具有一定的结晶性。     

Adhesion and Young’s Modulus Estimation for Chemically Treated Argan Nut Shell Particles Reinforced Poly-Lactic Acid Polymer

Abstract

The use of natural fillers as reinforcements for polymer plastics takes place in a variety of industrial applications. Henceforth, the use of theoretical models to predict the properties of such bio-composites is essential. In this work, we estimated the Young’s modulus of poly-lactic acid (PLA) bio-composites reinforced with argan nut shell (ANS) chemically treated particles (successive alkali treatment, bleaching and silane treatments) using five theoretical models and compared the predicted results with our prior experimental results. These models allowed us to study the assumed spherical form of the ANS particles and the adhesion/distribution of these particles in a PLA matrix. The results indicated that the ANS chemically treated particles could be considered as spherical particles having good adhesion with the PLA matrix. In addition, three other mathematical models were used to predict Young’s modulus of the ANS chemically treated particles. The results showed that the highest value of Young modulus among the three treatments was obtained for the ANS alkali-bleached particles. In addition, the silane treatment enhanced the adhesion between the ANS particles and the PLA matrix, but decreased the Young’s modulus value compared to the other two treatments.     

Physicochemical characteristic of neodymium oxide-based catalyst for in-situ CO2/H2 methanation reaction

Carbon dioxide emission to the atmosphere is worsened as all the industries emit greenhouse gases (GHGs) to the atmosphere, particularly from refinery industries. The catalytic chemical conversion through methanation reaction is the most promising technology to convert this harmful CO₂ gas to wealth CH₄ gas for the combustion. Thus, supported neodymium oxide based catalyst doped with manganese and ruthenium was prepared via wet impregnation route. The screening was initiated with a series of Nd/Al₂O₃ catalysts calcined at 400?°C followed by optimization with respect to calcination temperatures, based ratios loading and various Ru loading. The Ru/Mn/Nd (5:20:75)/Al₂O₃ calcined at 1000?°C was the potential catalyst, attaining a complete CO₂ conversion and forming 40% of CH₄ at 400?°C reaction temperature. XRD results revealed an amorphous phase with the occurrence of active species of RuO₂, MnO_2, and Nd₂O₃, and the mass ratio of Mn was the highest among other active species as confirmed by EDX. The ESR resulted in the paramagnetic of Nd³⁺ at the g value of 2.348. Meanwhile nitrogen adsorption (NA) analysis showed the Type IV isotherm which exhibited the mesoporous structure with H3 hysteresis of slit shape pores.     

Synergistic Effect of NiLDH@YZ Hybrid and Mechanochemical Agitation on Glaser Homocoupling Reaction

Herein, we report the synthesis of nickel-layered double hydroxide amalgamated Y-zeolite (NiLDH@YZ) hybrids and the evaluation of the synergistic effect of various NiLDH@YZ catalysts and mechanochemical agitation on Glaser homocoupling reactions. Nitrogen adsorption-desorption experiments were carried out to estimate the surface area and porosity of NiLDH@YZ hybrids. The basicity and acidity of these hybrids were determined by CO₂-TPD and NH₃-TPD experiments respectively and this portrayed good acid-base bifunctional feature of the catalysts. The NiLDH@YZ-catalyzed mechanochemical Glaser coupling reaction achieved best yield of 83 % for the 0.5NiLDH@0.5YZ hybrid after 60 min of agitation, which revealed the highest acid-base bifunctional feature compared to all the investigated catalysts. The developed catalyst has proven itself as a robust and effective candidate that can successfully be employed up to four catalytic cycles without significant loss in catalytic activity, under optimized reaction conditions. This work demonstrated a new strategy for C−C bond formation enabled by the synergy between mechanochemistry and heterogeneous catalysis.     

Multipole cross sections for collisional excitation of highly charged ions by isotropic electrons

The relativistic distorted-wave program of the flexible atomic code for calculating the cross sections for electron-impact excitation of ions between fine-structure levels is extended to get the multipole components of cross sections in the case of excitation by isotropic electrons. These components may be needed for interpreting the intensity and polarization of line emissions from thermal plasmas exposed to anisotropic radiations, such as the solar corona under photosphere irradiation. Illustrative numerical results are given for excitation of Si-like Fe¹²⁺ between the , and levels. These results can be useful in the analysis of infrared forbidden lines emitted from the solar corona. A comparison is made with the only published work based on the semi-relativistic distorted-wave approximation, showing some agreement for the excitation and discrepancies for the weak transition .