Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

Fe3O4-carbon spheres core–shell supported palladium nanoparticles: A robust and recyclable catalyst for suzuki coupling reaction

Suzuki-Miyaura (S-M) is regarded the most powerful way for synthesis biaryls, triaryls, or incorporating of substituted aryl moieties in organic preparation by the cross-coupling of aryl boronic acid with aryl halides using the Pd catalyst. This work reports the combining of the hydrothermal and microwave-assisted protocol to convert the glucose to magnetic carbon spheres (Fe₃O₄-CSPs) decorated with Pd nanoparticles (NPs) as the catalyst for Suzuki-Miyaura cross-coupling reactions. The physicochemical properties in the produced composite were examined using FESEM, HRTEM, nitrogen isotherms, Raman spectroscopy, FTIR, XPS, and XRD. The as-fabricated composite Pd/Fe₃O₄-CSPs is mostly spherical with a core–shell structure and possesses a great surface area of 253.2 m²·g^-1. Its catalytic performance demonstrates that the composite has excellent stability and high tolerance Suzuki-Miyaura cross-coupling reactions in 30 min at 80 ℃. Both activated and deactivated aryl halides provided excellent yield. The as-fabricated catalyst was recycled for up to four catalytic cycles without a substantial decline in performance. Moreover, this research offers a facile roadmap for synthesizing Pd/Fe₃O₄-CSPs composites and promoting the practical implementation of Pd/Fe₃O₄-CSPs catalysts for organic transformation processes.     

Alkoxyl side-chain effects of acidic ionic liquids catalysts for the esterification of n-butyl butyrate

Three kinds of alkoxy group-functionalized acidic ionic liquids (ILs) are reported in this work, namely, 1-(methoxyethyl)-3-methylimidazolium hydrogen sulphate [MOE-MIM]HSO₄, 1-(ethyoxyethyl)-3-methylimidazolium hydrogen sulphate [EOE-MIM]HSO₄, and 1-(propyoxyethyl)-3-methylimidazolium hydrogen sulphate [POE-MIM]HSO₄. The short side chain on the cation of [MOE-MIM]HSO₄ decreases the solubility of the IL in butanol and butyric acid and facilitates the separation of the IL from a reaction medium. The yield of butyl butyrate is up to 99.5%. After 10 rounds of recycling, the catalytic performance of [MOE-MIM]HSO₄ shows no significant changes.     

Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Hydrogen generation rate enhancement by in situ Fe(0) and nitroarene substrates in Fe3O4@Pd catalyzed ammonia borane hydrolysis and nitroarene reduction tandem reaction

We report the catalytic enhancement of hydrogen generation by 1) in situ Fe (0) formed and 2) nitroarenes substrates during Fe₃O₄@Pd core-shell nanoparticles catalyzed tandem reaction. The active hydrogen species are generated in Pd shell, which either combine to form H₂ gas or take part in relatively faster nitroarene reduction reaction. The rate of hydrogen generation from ammonia borane is dependent on the nitroarene substrate and is higher when 4-nitrophenol is used. This is due to the difference in ammonia borane adsorption on the surface of the catalyst. During recyclability, the H₂ generation rate of 2 wt% Pd loaded samples is higher than other compositions. Such an enhancement has been attributed to the formation of Fe (0) via γ-FeOOH mediated by Pd species, presumably through Pd(OH)₂. The electronic connection between Fe and Pd interface is thus shown to play an important role in the catalytic enhancement of the tandem reaction.     

Evaluation of the degree of rate control via automatic differentiation

The degree of rate control (DRC) quantitatively identifies the kinetically relevant (sometimes known as rate-limiting) steps of a complex reaction network. This concept relies on derivatives which are commonly implemented numerically, for example, with finite differences (FDs). Numerical derivatives are tedious to implement, and can be problematic, and unstable or unreliable. In this study, we demonstrate the use of automatic differentiation (AD) in the evaluation of the DRC. AD libraries are increasingly available through modern machine learning frameworks. Compared with the FDs, AD provides solutions with higher accuracy with lower computational cost. We demonstrate applications in steady-state and transient kinetics. Furthermore, we illustrate a hybrid local-global sensitivity analysis method, the distributed evaluation of local sensitivity analysis, to assess the importance of kinetic parameters over an uncertain space. This method also benefits from AD to obtain high-quality results efficiently.     

氮杂环卡宾-钯功能化的配位聚合物（NHC-Pd@Zn-L）：合成、表征及催化Suzuki-Miyaura交叉偶联反应

以\mathrm{1,3}-二(1-羧乙基)咪唑盐(HL)和Zn(NO₃)₂·6H₂O反应合成二维配位聚合物[Zn(L)₂] _n (Zn-L)，产物再与K₂PdCl₄在四氢呋喃溶液中反应引入氮杂环卡宾-钯（NHC-Pd）催化位点，制得催化剂NHC-Pd@Zn-L，并通过PXRD、TGA、ICP、SEM、EDS和XPS进行表征。结果表明，NHC-Pd@Zn-L具有良好的热稳定性且修饰后晶体的框架结构没有发生变化，Pd以NHC-Pd的形式结合在Zn-L中，并均匀分散在配位聚合物中。将NHC-Pd@Zn-L用于催化Suzuki-Miyaura交叉偶联反应，当以苯硼酸和溴苯为底物，催化剂用量为15 mg，乙醇为溶剂，碳酸钾为碱的条件下60℃反应6 h，产率达到>99%，而且催化剂易于回收并可循环使用3次。     

羟基磷灰石作为催化材料的研究进展

羟基磷灰石(HAP)由于具有无毒性、生物相容性、热稳定性、吸附性、离子交换性、结构稳定性等,因而被广泛应用到催化剂的制备中。作为一种新型催化材料,HAP的特殊晶体结构对一些反应表现出催化活性,并且经过改性、负载等方法处理过后的HAP催化剂显示出独特的催化优势。基于近年来HAP在催化邻域的发展,综述了HAP作为催化材料在降解污染物、制氢、药物合成、还原氮氧化物等反应中的不同应用,并对未来的研究方向进行了展望。     

TiO2上的CuAg纳米粒子用于高效乙醛光降解

光降解乙醛(CH3CHO)是一种新型高效的乙醛去除方法，通常采用TiO2作为光催化剂。然而TiO2对乙醛吸附能力较弱，对产物的选择性较低，电子-空穴对重组率较高，严重限制了对乙醛的降解性能。本研究通过在TiO2上负载CuAg纳米粒子(CuAg/TiO2)，成功构建了高效稳定的光催化降解乙醛催化剂，有效解决了TiO2的固有缺陷。在自然光照射下，CuAg/TiO2对乙醛的降解率高达42.49%。连续4轮全光谱光催化降解乙醛，CuAg/TiO2活性均保持在98.89%以上。进一步的机理研究表明，CuAg/TiO2中的CuAg纳米粒子在光照下产生热电子，随后热电子转移到TiO2和吸附在Ag位点上的氧中。CuAg/TiO2上生成的超氧自由基能有效地降解乙醛，从而在乙醛降解过程中表现出优异的性能。