Lewis Acid Transition-Metal-Catalyzed Hydrogen Activation: Structures,Mechanisms, and Reactivities

As a new type of bifunctional catalyst, the Lewis acid transition-metal (LA-TM) catalysts have been widely applied for hydrogen activation. This study presents a mechanistic framework to understand the LA-TM-catalyzed H₂ activation through DFT studies. The mer(trans)-homolytic cleavage, the fac(cis)-homolytic cleavage, the synergetic heterolytic cleavage, and the dissociative heterolytic cleavage should be taken as general mechanisms for the field of LA-TM catalysis. Four typical LA-TM catalysts, the Z-type κ⁴-L₃B-Rh complex tri(azaindolyl)borane-Rh, the X-type κ³-L₂B-Co complex bis-phosphino-boryl (PBP)-Co, the η²-BC-type κ³-L₂B-Pd complex diphosphine-borane (DPB)-Pd, and the Z-type κ²-LB-Pt complex (boryl)iminomethane (BIM)-Pt are selected as representative models to systematically illustrate their mechanistic features and explore the influencing factors on mechanistic variations. Our results indicate that the tri(azaindolyl)borane-Rh catalyst favors the synergetic heterolytic mechanism; the PBP-Co catalyst prefers the mer(trans)-homolytic mechanism; the DPB-Pd catalyst operates through the fac(cis)-homolytic mechanism, whereas the BIM-Pt catalyst tends to undergo the dissociative heterolytic mechanism. The mechanistic variations are determined by the coordination geometry, the LA-TM bonding nature, the electronic structure of the TM center, and the flexibility or steric effect of the LA ligands. The presented mechanistic framework should provide helpful guidelines for LA-TM catalyst design and reaction developments.     

A Near-Infrared-Controllable Artificial Metalloprotease Used for Degrading Amyloid-β Monomers and Aggregates

Proteolysis of amyloid-β (Aβ) is a promising approach against Alzheimer's disease. However, it is not feasible to employ natural hydrolases directly because of their cumbersome preparation and purification, poor stability, and hazardous immunogenicity. Therefore, artificial enzymes have been developed as potential alternatives to natural hydrolases. Since specific cleavage sites of Aβ are usually embedded inside the β-sheet structures that restrict access by artificial enzymes, this strongly hinders their efficiency for practical applications. Herein, we construct a NIR (near-IR) controllable artificial metalloprotease (MoS₂-Co) using a molybdenum disulfide nanosheet (MoS₂) and a cobalt complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (Codota). Evidenced by detailed experimental and theoretical studies, the NIR-enhanced MoS₂-Co can circumvent the restriction by simultaneously inhibition of β-sheet formation and destroying β-sheet structures of the preformed Aβ aggregates in living cell. Furthermore, our designed MoS₂-Co is an easy to graft Aβ-target agent that prevents misdirected or undesirable hydrolysis reactions, and has been demonstrated to cross the blood brain barrier. This method can be adapted for hydrolysis of other kinds of amyloids.     

Hydrogen-Bond Cyclization Programming of Ultrasensitive Esters and Its Application in Gene Delivery

The ester bond as a universal linker has recently been applied in gene delivery systems owing to its efficient gene release by electrostatic repulsion after its cleavage. However, the ester bond is nonlabile and is difficult to cleave in cells. This work reports a method in which a secondary amine was introduced to the β-position of the ester bond to generate a hydrogen-bond cyclization (HBC) structure that can make the ester bond hydrolysis ultrafast. A series of molecules comprising ultrasensitive esters that can be activated by H₂O₂ were synthesized, and it was found that those able to form an HBC structure showed complete ester hydrolysis within 5 h in both water and phosphate-buffered saline solution, which was several times faster than other methods reported. Then, a series of amphiphilic poly(amidoamine) dendrimers were constructed, comprising the ultrasensitive ester groups for gene delivery; it was found that they could effectively release genes under quite a low concentration of H₂O₂ (<200 μm ) and transport them into the nucleus within 2 h in Hela cells with high safety. Their gene transfection efficiencies were higher than that of PEI_25k. The results demonstrated that the hydrogen-bond-induced ultrasensitive esters could be powerfully applied to construct gene delivery systems.     

Fabrication of large-scale ripples on fluorine-doped tin oxide films by femtosecond laser irradiation

The large-scale uniform self-organized ripples are fabricated on fluorine-doped tin oxide （FTO） coated glass by femtosecond laser. They can be smoothly linked in a horizontal line with the moving of XYZ stage by setting its velocity and the repetition rate of the laser. The ripple-to-ripple linking can also be realized through line-by-line scanning on a vertical level. The mechanism analysis shows that the seeding effect plays a key role in the linking of ripples.     

An efficient,scalable approach to hydrolyze flavonoid glucuronides via activation of glycoside bond

Hydrolyzing flavonoid glucuronides into corresponding aglycones posed some significant challenges. To improve acid-catalyzed hydrolysis process of flavonoid glucuronide, structures of glucuronide, hydrolysis parameters and post-processing were optimized. The optimized condition was performed by hydrolysis flavonoid glycoside methyl ester in a mixed solvent consisting of 2 mol/L H₂SO₄/EtOH/H₂O (1/8/1, v/v/v) at 95 °C for 7 h and resulted in up to 90% aglycone yields, minimal byproduct formations and milder hydrolysis conditions. Furthermore, the optimized method avoids tedious purification steps and is easily conducted on a relatively large-scale using economical and commercially available reagents.     

Mn-Fe_2O_3载氧体作用下CO化学链燃烧特性及动力学研究

采用共沉淀法制备不同物质的量比Mn掺杂的铁基载氧体(Mn-Fe2O3),并进行XRD、BET和TEM表征。开展不同温度下Mn-Fe2O3与CO的化学链燃烧实验,研究载氧体的反应特性,确定较优的掺杂量和反应温度。结果表明,适量的Mn掺杂有助于改善铁基载氧体的反应活性,Fe∶Mn物质的量为50∶1时燃烧反应转化率最高。多循环化学链燃烧实验证实了载氧体稳定性较好。不同升温速率(30、40、50℃/min)下反应动力学分析表明,Mn-Fe2O3与CO的化学链燃烧还原反应均属于随机成核和随后生长的Avrami-Erofeev方程模型,并依据模型分别计算出了该模型的活化能和频率因子。