Design and synthesis of the honeycomb PtSnNa/ZSM-5 monolithic catalyst for propane dehydrogenation

A novel PtSnNa/ZSM-5 monolithic catalyst was designed and synthesized for the propane dehydrogenation reaction, which was a significant transformation in industry. Experimental results showed that although the propane conversion and the propylene selectivity gradually fell down along with the reaction time, the descent speed of the PtSnNa/ZSM-5 monolithic catalyst was slower than that of the granule catalyst and the propane conversion and propylene selectivity of the reaction with monolithic catalyst still remained at a high level after 12 hr. The monolithic catalyst had regular pore structure that facilitated the separation of the product from the catalyst and reduced the limitation on internal and external diffusion and mass transfer, and led to the high catalytic activity and stability. The catalyst could be easily fabricated and was of highly industrial application potential.     

Preparation of an efficient catalyst through injection of CuI on modified poly (styrene-co-maleic anhydride) and theoretical investigation of the structural and electronic properties of catalyst

A novel polymer supported [poly (styrene-co-maleic imide) (SMI)]Cu(I) nano-particles was prepared via in situ reaction of 4-amino-5-methyl-4H-1,2,4-triazole-3-thione with [poly (styrene-co-maleic anhydride)] (SMA) along with immobilization of CuI. These nano-particles were fully characterized by using scanning electron microscopy (SEM), energy dispersive spectroscopy analysis, Xray (EDAX), inductively coupled plasma (ICP) analysis, ¹H NMR and FT-IR techniques. Moreover, the structural and electronic features of metal–ligand interactions in the complex model of polymer-supported copper nanocatalyst were assessed using density functional theory calculations. The catalytic activity of these supported Cu(I) nonoparticles was examined in one of the classiest name reaction so–called “click reaction” which is coined K. B Sharpless for the regioselective synthesis of 1,2,3-triazole derivatives using a multicomponent reaction (MCR) involving benzyl halides, sodium azide and terminal alkynes in water as a green solvent. This heterogeneous catalyst showed excellent catalytic activity and was separated by simple filtration and was used at least in five consecutive runs without a significant decrease in its activity.     

A theoretical study on the pure and doped ZnO nanoclusters as effective nanobiosensors for 5-fluorouracil anticancer drug adsorption

The electronic sensitivity and effectiveness of the pristine, Fe,- Mg-, Al- and Ga-doped ZnO nanoclusters interacted with 5-fluorouracil (5-FU) anticancer drug are theoretically investigated in the gas phase using the B3LYP/wB97XD density functional theory calculations with LANL2DZ basis set. It is concluded that 5-FU adsorption on the doped nanoclusters has relatively higher adsorption energy as compared with the pristine zinc oxide. A number of thermodynamic parameters, such as band gap energy (E_g), adsorption energy (E_ad), molecular electrostatic potential, global hardness (η) and density of electronic states, are attained and compared. Also, calculated geometrical parameters and electronic properties for the studied systems indicate that Mg- and Ga-doped Zn₁₂O₁₂ present higher sensitivity to 5-FU compared with the pristine nanocluster. Theoretical results reveal that adsorption of 5-FU on the doped nanoclusters is influenced by the electronic conductance of the nanocluster. Therefore, Mg- and Ga-doped ZnO can be considered as promising nanobiosensors for detection of 5-FU in medicine.     

Anticancer activity of lanthanum (III) and europium (III) 5-fluorouracil complexes on Caco-2 cell line

Lanthanide complexes are of increasing importance in cancer diagnosis and therapy. In the present study 1:1 and 1:3 solid complexes of La (III)–5-FU (5-fluorouracil) were prepared and characterized. In solution, the formation of 1:1 La (III) and Eu (III) complexes enabled the enhancement of 5-FU's effectiveness. Binding constants of the 1:1 complexes of both metals were estimated using spectrophotometry and HPLC with fluorescence detection methods. The thermodynamic parameters ΔG ^° , ΔH ^° and ΔS ^° were calculated using differential scanning calorimetry. Evaluation of the cytotoxic activity of the 1:1 La (III)- and Eu (III)–5-FU complexes was performed through two methodologies, trypan blue for cell viability where La (III)- and Eu (III)–5-FU complexes were found to have 52,000 and 80,000 dead cells, respectively, and via flow cytometric analysis to measure the apoptotic values, which were found to be 59.87 and 86.86% respectively.     

Investigating the kinetics of liquid-free,OSDA-free ZSM-5 zeolite synthesis from iron ore tailings

In this study, ZSM-5, which is a Mobil-type five-type zeolite with well-defined crystal morphology, is successfully synthesized via a seed-assisted, liquid-free method that uses iron ore tailings as a silica source. The ZSM-5 crystallization kinetics at 423, 433, and 443 K and different synthesis times are investigated to identify the nucleation and crystallization mechanisms of the synthesized ZSM-5 zeolites, and results suggest that the crystallization kinetics follow a Kolmogorov-Johnson-Mehl-Avrami-type behavior. The activation energies for the induction and transition periods are 112.38 and 58.35 kJ mol⁻¹, respectively. Furthermore, the Avrami exponent indicates three-dimensional crystal growth from both sporadic and instantaneous nucleation mechanisms. A comparison of our results with previous reports of the ZSM-5 crystallization mechanism demonstrates that the seed crystals play a significant role in nucleation and crystal growth. Finally, seed surface crystallization and new nuclei crystallization dual mechanism has been proposed to describe the crystallization process of ZSM-5.     

基于5-磺基水杨酸的单、双核铜(Ⅱ)三元混配配合物的合成及晶体结构

以5-磺基水杨酸和咪唑衍生物为配体合成了单核、双核结构的三元混配Cu(Ⅱ)配合物:[Cu(H₂biim)(Hssal)(H₂O)₂]·H₂O(1)和{[Cu(MeHbiim)(Hssal)(H₂O)]·0.5H₂O}₂(2)(H₃ssal=5-磺基水杨酸,H₂biim=2,2’-联咪唑,MeHbiim=N-甲基-2,2’-联咪唑),并利用元素分析、红外光谱、紫外-可见光谱、X-射线单晶衍射及热重分析等技术手段对其结构进行了表征。单晶结构解析表明配合物1属于单斜晶系,P2₁／C 空间群,Cu(Ⅱ)离子与1个5-磺基水杨酸根、2个水分子以及1个联咪唑分子形成五配位四角锥构型的单核配合物结构。配合物2属于正交晶系,P2(1)2(1)2(1)空间群,双核Cu(II)离子分别处于五配位四角锥和四配位平面四边形的几何构型的配位环境中,与配合物1不同,5-磺基水杨酸采取μ₂双-单齿配位模式。荧光光谱分析表明配合物2具有较强的荧光性。     

Theoretical studies of the concentration dependences of d–d transition band,g factors,and local distortion for V4+ in Li2O–PbO–B2O3–P2O5 glasses

In this work, the g factors, d–d transition band, local distortion, and their concentration dependences for impurity V⁴⁺ in 20Li₂O–20PbO–45B₂O₃–(15 − x)P₂O₅:V₂O₅ (0 ≤ x ≤ 2.5 mol%) glasses are theoretically investigated by using perturbation formulas of g factors for a tetragonally compressed octahedral 3d¹ cluster. In the light of the cubic polynomial concentration functions for cubic field parameter D_q, covalency factor N, and relative tetragonal compression ratio ρ, the calculated concentration dependences of d–d transition band and g factors for V⁴⁺ show good agreement with the experimental data. With increasing x, N (≈0.7682–0.8165) displays the monotonously increasing trend, whereas ρ (≈6.5–4.2%) and D_q (≈1504.9–1481.1 cm⁻¹) exhibit the decreasing tendencies. The above concentration dependences can be ascribed to the modifications of the V⁴⁺–O²⁻ bonding and orbital admixtures around the impurity V⁴⁺ due to the effects of V₂O₅ doping on the stability of the glass network, the strength of local crystal fields, and the electron cloud distribution.     

Dynamic materials derived from biobased furans: towards the ‘sleeping giant’ awakening

This focus article presents the author’s view on the problems in the development of biorefining strategies based on the use of 5-(hydroxymethyl)furfural (HMF), the key product derived from renewable plant biomass that was recognized as the ‘sleeping giant’ of the sustainable chemistry. The several key problems that hinder the large-scale production of HMF and its applicability in the laboratory organic synthesis and industry are discussed. This minireview is also focused on the development of the dynamic cross-linked polymers with controlled three-dimensional structure based on Diels–Alder reaction of biobased HMF-derived furans with maleimides. Realization of scalable technologies for an efficient production of such ‘smart’ analogues of the traditional petrochemical-based materials could be the basis for the realization of the competitive HMF-promoted biorefining.     

基于结构虚拟筛选发现蛋白质精氨酸甲基转移酶5抑制剂

蛋白质精氨酸甲基转移酶5(PRMT5)是蛋白质甲基转移酶家族(PRMTs)的重要一员,其主要生理功能是催化精氨酸单对称二甲基化。PRMT5的上调发生在不同类型的肿瘤中,并与不良预后密切相关,已被视为肿瘤治疗中的潜在靶点。近年来,已有多种PRMT5抑制剂进入临床试验,但目前尚未有药物获批上市。本研究基于Glide对接的虚拟筛选和生物活性实验,发现化合物8018-1271对PRMT5酶的抑制活性IC₅₀值为13.56±0.86μmol/L,并通过分子动力学揭示其与PRMT5蛋白结构域的相互作用模式。本研究所得化合物8018-1271可作为进一步改造的先导化合物,为新型PRMT5抑制剂的发现提供参考。     

Synthesis and cytotoxicity studies of new 1,2,4-thiadiazole derivatives and their zinc complexes

A new polyfunctional ligand of the thiadiazole family was synthesized. Cytotoxic properties with respect to leukemic cell lines, radiation stability, predicted permeability through the blood–brain barrier and cardiotoxicity of the new ligand and its precursor were determined. New zinc complexes with N-{2-[5-(3-chloro-4-methylphenylamino)-1,2,4-thiadiazol-3-yl]-1-methylethyl}-N-(2,2,6,6-tetramethylpiperidin-4-yl)-amine as the ligand have been obtained.