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.     

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.     

Alteration of the Route to Menaquinone towards Isochorismate-Derived Metabolites

Chorismate and isochorismate constitute branch-point intermediates in the biosynthesis of many aromatic metabolites in microorganisms and plants. To obtain unnatural compounds, we modified the route to menaquinone in Escherichia coli. We propose a model for the binding of isochorismate to the active site of MenD ((1R,2S, 5S,6S)-2-succinyl-5-enolpyruvyl-6-hydroxycyclohex-3-ene-1-carboxylate (SEPHCHC) synthase) that explains the outcome of the native reaction with α-ketoglutarate. We have rationally designed variants of MenD for the conversion of several isochorismate analogues. The double-variant Asn117Arg–Leu478Thr preferentially converts (5S,6S)-5,6-dihydroxycyclohexa-1,3-diene-1-carboxylate (2,3-trans-CHD), the hydrolysis product of isochorismate, with a >70-fold higher ratio than that for the wild type. The single-variant Arg107Ile uses (5S,6S)-6-amino-5-hydroxycyclohexa-1,3-diene-1-carboxylate (2,3-trans-CHA) as substrate with >6-fold conversion compared to wild-type MenD. The novel compounds have been made accessible in vivo (up to 5.3 g L⁻¹). Unexpectedly, as the identified residues such as Arg107 are highly conserved (>94 %), some of the designed variations can be found in wild-type SEPHCHC synthases from other bacteria (Arg107Lys, 0.3 %). This raises the question for the possible natural occurrence of as yet unexplored branches of the shikimate pathway.     

催化裂化汽油光化学氧化脱硫

以水为萃取剂、空气中的O2为氧化剂、500W高压汞灯为紫外光光源,研究了催化裂化(FCC)汽油光化学氧化反应的机理和氧化产物,考察了反应条件对FCC汽油脱硫率的影响。实验结果表明,FCC汽油中的极性含硫化合物首先部分溶于水相中,然后在水相中被氧化。在空气通入量为150mL/min、水与FCC汽油的体积比为1.0的条件下,反应5h后FCC汽油脱硫率达40.6%,加入0.45g4A分子筛作为O2的吸附剂后FCC汽油脱硫率提高到70.2%。FCC汽油的光化学氧化反应为一级动力学反应,加入4A分子筛时的反应速率常数为0.217 4h-1,半衰期为3.18h。FCC汽油光化学氧化反应的主要产物为亚砜和砜,并进一步生成CO2、草酸、SO24-等。     

分子印迹技术及其应用

分子印迹技术是将高分子科学、材料科学、生物学、化学工程等有机集成。基于分子印迹技术所制备的分子印迹聚合物具有选择性高、稳定性好、应用范围广等特点 ,近年来得到了日益广泛和深入的研究。介绍了分子印迹技术的原理、分子印迹聚合物的制备方法、分子印迹技术的应用场合和实例 ,并简要预测了分子印迹技术领域未来的发展趋势。