Modulated synthesis of cesium phosphomolybdate encapsulated in hierarchical porous UiO-66 for catalysing alkene epoxidation.

The hybrid composite of cesium phosphomolybdate (CsPM) encapsulated in hierarchical porous UiO-66 (HP-UiO-66) was synthesized using a modulated solvothermal method. A variety of characterization results demonstrated that the pore size distribution of CsPM@HP-UiO-66 is broader than traditional microporous CsPM@UiO-66 and cesium phosphomolybdate clusters are uniformly distributed in the octahedral cages of HP-UiO-66. The catalytic properties of the hybrid composite were investigated in alkene epoxidation reaction with tert-butyl hydroperoxide (t-BuOOH) as an oxidant. CsPM@HP-UiO-66 showed much higher catalytic activity for the alkene epoxidation reaction in comparison with the reference catalysts and could be easily reused by centrifugation and recycled for at least ten runs without significant loss in catalytic activity. The superior catalytic activity and stability of the hybrid composite CsPM@HP-UiO-66 should be mainly attributed to the hierarchical pores in the support HP-UiO-66 promoting the diffusion of alkene molecules, the uniform distribution of highly active CsPM clusters in the octahedral cages of HP-UiO-66, the introduction of cesium cations to form the insoluble cesium phosphomolybdate and the strong metal-support interactions (SMSI) between the CsPM clusters and the HP-UiO-66 framework.

Boosting the catalysis of cesium phosphomolybdate encapsulated in hierarchical porous UiO-66 by microenvironment modulation for epoxidation of alkenes.

The chemical microenvironment of polyoxometalates (POMs) encapsulated in metal-organic frameworks (MOFs) presents a significant influence on their catalytic performance, which can be easily regulated by the linker functional group alteration or metal substitution in MOFs. Herein, a series of cesium phosphomolybdate (CsPM) encapsulated in hierarchical porous UiO-66-X composites (CsPM@HP-UiO-66-X, X = H, 2CH3, or 2OH, where X represents the alterable group grafted onto the linker benzene ring) were successfully synthesized through a one pot modulated solvothermal method. The catalytic performances of the obtained materials were explored in alkene epoxidation reaction with tert-butyl hydroperoxide (t-BuOOH). CsPM@HP-UiO-66-2CH3 showed relatively high catalytic activity, stability, and epoxidation selectivity in cyclooctene epoxidation among the CsPM@HP-UiO-66-X composites. Moreover, CsPM@HP-UiO-66-2CH3 was effective in the epoxidation of numerous alkenes, especially cyclic alkenes. The superior catalytic activity of CsPM@HP-UiO-66-2CH3 is mainly attributed to the modulation of the microenvironment surrounding CsPM active sites by introducing a hydrophobic methyl group. Meanwhile, the size-matched effect, the introduction of cesium cations, and the strong metal-support interactions (SMSIs) between CsPM and HP-UiO-66-2CH3 play a crucial role in the stability of CsPM@HP-UiO-66-2CH3.

Methionine-Derived Organogels as Lubricant Additives Enhance the Continuity of the Oil Film through Dynamic Self-Healing Assembly.

(S)-2-((1-(Hexadecylamino)-4-(methylthio)-1-oxobutan-2-yl)carbamoyl)benzoic acid (HMTA) was efficiently synthesized and successfully applied as an additive to several types of blank lubricant oils. Initially, HMTA self-assembles to fibrous structures and traps blank lubricant oils to form gel lubricants. The prepared gel lubricants show thermo-reversible properties and enhanced lubricating performance by 3∼5-fold. X-ray photoelectron spectrometry of the metal surface and the quartz crystal microbalance illustrated that there are no obvious interactions between HMTA and the metal surface. The results of Fourier transform infrared spectroscopy and X-ray diffraction further confirm that inter/intro-molecular H-bonding interactions are the main driving force for the self-healing of HMTA. Finally, molecular dynamics (MD) simulations show that the number of noncovalent H-bonding interactions fluctuates with time, and this highly dynamic H-bonding network could regulate the self-assembly process and result in the self-healing property of the HMTA organogel, which is consistent with the results of the step-strain tests. Especially, the Hirshfeld independent gradient model method at the quantum level demonstrated that C8/C9 aromatics of 500SN have strong π-π stacking interactions with the aromatic heads of HMTA and van der Waals interactions with the hydrophobic tails of HMTA, which disrupt the self-assembly behavior of the 500SN model. Therefore, the calculation studies offer a rational explanation for the superior lubricant property of the PAO10 gel as compared to that for 500SN.

Controlling the Morphology and Titanium Coordination States of TS-1 Zeolites by Crystal Growth Modifier.

Developing an effective strategy to synthesize perfect titanosilicate TS-1 zeolite crystals with desirable morphologies, enriched isolated framework Ti species, and thus enhanced catalytic oxidation properties is a pervasive challenge in zeolite crystal engineering. We here used an amino acid l-carnitine as a crystal growth modifier and ethanol as a cosolvent to regulate the morphologies and the Ti coordination states of TS-1 zeolites. During the hydrothermal crystallization process, the introduced l-carnitine can not only tailor the anisotropic growth rates of zeolite crystals but also induce the formation of uniformly distributed framework Ti species through building a suitable chemical interaction with the Ti precursor species. Condition optimizations could afford the generation of perfect hexagonal plate TS-1 crystals and elongated platelet TS-1 crystals enriched in tetrahedral framework Ti sites (TiO4) or mononuclear octahedrally coordinated Ti species (TiO6). Both samples showed significant improvement in catalytic activity for the H2O2-mediated epoxidation of alkenes. In particular, the elongated platelet TS-1 enriched in "TiO6" species afforded the highest activity in 1-hexene epoxidation, with a turnover frequency (TOF) of up to 131 h-1, which is approximately twice as high as that of the conventional TS-1 zeolite (TOF: 65 h-1) and even higher than those of the literature-reported TiO6-containting TS-1 catalysts derived from the hydrothermal post-treatment of TS-1 zeolites. This work demonstrates that the morphologies and the titanium coordination states of TS-1 zeolites can be effectively tuned by directly introducing suitable crystal growth modifiers, thus providing new opportunities for developing highly efficient titanosilicate zeolite catalysts for important catalytic applications.

Protective Effects of Apocynum venetum Against Pirarubicin-Induced Cardiotoxicity.

Pirarubicin (THP) is an anthracycline antibiotic, frequently used for the treatment of various human cancers. Unfortunately, the clinical effectiveness of THP is limited by its dose-related cardiotoxicity. Apocynum leaf extract is an extract of the dried leaves of Apocynum venetum L. (a member of the Apocynaceae family, AVLE) that has many positive effects on the cardiovascular system and is widely consumed as tea in China. In this study we established a cardiactoxicity rat model, which showed that pretreatment with AVLE attenuated THP-induced myocardial histopathological injury, electrocardiogram abnormalities, and cardiac dysfunction. AVLE also significantly reduced serum levels of malondialdehyde (MDA), brain natriuretic peptide (BNP), creatine kinase (CK-MB), cardiac troponin (CTnT), and lactate dehydrogenase (LDH); and increased serum superoxide dismutase (SOD) levels. Treatment with AVLE or dexrazoxane (DZR) resulted in an increase Cytochrome C (cytc) in the mitochondria and reduced Cytc and cleaved-caspase-3 levels (p<0.05) in cytoplasm. We also found that AVLE significantly reduced voltage-dependent anion channel 1 (VDAC1), adenosine nucleotide transporter 1 (ANT1), and cyclophilin D (CYPD) mRNA expression (p<0.05). Furthermore, AVLE appeared to exert therapeutic effects in a dose-dependent manner. Our study suggests the anti-oxidant and anti-apoptotic properties of AVLE may be responsible for the observed cardioprotective effects.

Hybrid compounds assembled from copper-triazole complexes and phosphomolybdic acid as advanced catalysts for the oxidation of olefins with oxygen.

Two hybrid compounds, namely [Cu(3atrz)4][PMoMoVO40] (1) and [Cu(3atrz)6][PMo12O40]2 (2), were synthesized through hydrothermal reactions of 3-amino-1,2,4-triazole (3atrz), phosphomolybdic acid (PMA) and appropriate copper salts. Crystal structure analysis reveals that compound 1 contains one-dimensional Cu-3atrz chains. The unit of compound 2 contains a double calyx[3]arene-shaped hexamer, which is composed of six two-coordinated CuI atoms and six 3atrz ligands. Both compounds 1 and 2 present a three-dimensional hybrid structure, which is built by the self-assembly of Cu-3atrz clusters and Keggin-type PMA units. The resulting hybrid compounds can act as highly efficient heterogeneous catalysts for the selective oxidation of olefins with molecular oxygen as the oxidant in the presence of a trace amount of tert-butyl hydroperoxide (t-BuOOH). Their excellent catalytic properties can be mainly attributed to the existence of stabilized CuI complexes with an appropriate chemical environment and a spacious structure, which can interact with t-BuOOH to form catalytic sites for the direct activation of O2. This work demonstrates that the hybrid compounds assembled from copper-3atrz complexes and phosphomolybdic acid may have great potential in molecular O2-mediated catalytic oxidation reactions, which can certainly build a platform for deep insight into the biologically relevant catalytic oxidation processes.