伴有辅酶再生的生物催化过程

很多生物催化的氧化还原反应需要昂贵辅酶的参与,本文详细介绍了伴有辅酶再生的生物催化过程中,辅酶的使用、辅酶的酶反应再生、电化学再生及载体再生的特点,并对各种再生方法的优缺点进行了比较,同时介绍了辅酶的固定化及化学改性方法的研究进展.简单综述了伴有辅酶再生的基于细胞、游离酶和固定化酶的生物催化系统的研究和应用,并展望了辅酶的研究前景及辅酶再生研究的发展方向和亟待解决的问题.     

辅酶NAD(P)H模型分子的研究进展

辅酶NAD(P)H在生物体内起着重要的调节作用, 已引起了有机化学工作者极大的兴趣, 尤其是在还原反应的立体选择性上, 人们已经开展了大量的研究工作. 讨论了NAD(P)H模型分子进行立体专一性还原反应的影响因素, 并对NAD(P)H模型分子的研究工作做了总结.     

重金属离子的光催化还原研究进展

近些年来,光催化氧化还原用于环境污染消除方面已经得到了较为广泛的研究。其中,关于有机污染物的光催化氧化降解研究较多,其综述文章也屡见报道。在对有机污染物进行氧化研究的同时,也有一些关于有毒金属离子光催化还原的报道,但还未见有相关的综述,本文主要就重金属离子的光催化还原给以综述。     

烟酰型辅酶NAD(P)+和NAD(P)H再生的研究进展

大部分氧化还原酶的催化反应需要烟酰型辅酶NAD(P) 和NAD(P)H作为氧化剂或还原剂参与,由于氧化还原酶应用广泛而辅酶价格昂贵,使得辅酶再生逐渐成为研究热点.综述了近年来NAD(P) 和NAD(P)H酶法再生、电化学法及光化学法再生的研究进展,并介绍了各再生技术的应用和开发状况.     

NAD（P）H辅酶模型物结构与反应性关系的研究

合成了一系列３－酰胺基氮取代的ＮＡＤ（Ｐ）Ｈ模型物,测定了其与５－硝基异喹啉正离子的二级反应速度常数,并一模型物的氧化还原电势进行了比较,实验结果表明,模型闰酰基氧－方面可离域二氢吡啶环上Ｎ的电子;另一方面负一的３－位酰基氧在反应过渡态中又可引起分子内和分子间的两种静电作用;３－位酰基的电子效应对模型物动力学反应性的影响是这两种效应综合作用的结果。     

光激发电荷在光催化氧化还原反应中的全利用（英文）

光催化转化CO₂为碳氢燃料,分解水产氢,选择性有机合成,还原N₂为NH₃,降解毒害的有机污染物等对解决能源环境问题有重要意义。早在1972年,研究者利用TiO₂通过光催化实现了全面分解水产氢和产氧。由于低的可见光利用率,严重的载流子复合和过高的水氧化能垒导致光催化全面水分解的效率极低。由于氢相对于氧更具有经济价值,因此牺牲剂辅助的光催化产氢被大量研究。由于牺牲剂可以快速的消耗光生空穴,有效降低了氧化端的能垒,光催化产氢的效率相比于光催化水分解的效率提高了3–4个量级。然而,牺牲剂的使用不仅导致了光生空穴的浪费,成本的提高,还导致了潜在的环境问题。近些年,研究者通过将光催化还原反应和光催化氧化反应结合在一起实现了电子空穴的全面利用,并改进了氧化和还原的效率。同时,电子空穴的全面利用也有效的促进了电荷的分离并提高了催化剂的稳定性。然而,由于全面氧化还原的设计难度大,反应过程复杂,因此光催化全面氧化还原的机理尚不够明确,仍然需要大量的探索。在这篇综述中,首先从光捕获、光激发电荷分离、氧化还原反应的热力学和...     

构建光催化氧化-还原体系的研究进展

光催化氧化-还原体系能够同时驱动光催化氧化反应和还原反应,产生协同效应,从而提高光催化反应的活性。在此,提出了构建光催化氧化-还原体系的原则,并介绍了光催化还原硝基芳烃耦合氧化有机物、光催化还原重金属离子协同氧化有机物、光解水制氢协同氧化有机物三个方面的实例。接着,阐述了光催化氧化-还原体系的反应机理,期望通过构建光催化氧化-还原体系,更有利于太阳能转化并缓解环境和能源问题。     

煤质活性炭的光催化再生

 研究了利用光催化氧化降解反应实现饱和吸附苯酚的煤质活性炭光催化再生的可行性，并分析了活性炭的光催化再生机理．结果表明，在一定条件下可以实现活性炭的光催化再生．在Ag－TiO2负载量为1．9％，pH＝13，θ＝70℃，t＝72h的再生条件下，活性炭的再生率可达 78．4％．在光照条件下，光催化剂作为有机物的降解中心而造成活性炭内外吸附苯酚的浓度差是活性炭光催化再生的主要驱动力．     

Towards Recyclable NAD(P)H Regeneration Catalysts

Rh(III)-TsDPEN, an immobilized analog of the well-known [Cp*Rh(bpy)(H₂O)]²⁺ was evaluated as a heterogeneous, recyclable regeneration catalyst for reduced oxidoreductase cofactors [NAD(P)H]. Repeated use of this catalyst was established and the catalytic properties were initially investigated. Apparently, Rh(III)-TsDPEN is prone to severe diffusion limitations, necessitating further developments. Overall, a promising concept for chemoenzymatic redox catalysis is proposed, which may overcome some of the current limitations such as catalyst cost and incompatibility of Rh with some biocatalysts.     

Enzyme-Compatible Core-Shell Nanoreactor for in Situ H2-Driven NAD(P)H Regeneration

The regeneration of the reduced form cofactor NAD(P)H is essential for the extra-cellular application of bio-reduction, which necessitates not only the development of efficient artificial NAD(P)H regeneration catalytic system but also its well compatibility with the cascade enzymatic reduction system. In this work, we reported the preparation of a metal nanoparticle (NP) and metal complex integrated core-shell nanoreactor for H₂-driven NAD(P)H regeneration through the immobilization of a Rh complex on Ni/TiO₂ surface via a bipyridine contained 3D porous organic polymer (POP). In comparison with the corresponding single component metal NPs and the immobilized Rh complex, the integrated catalyst presented simultaneously enhanced activity and selectivity in NAD(P)H regeneration thanks to the rapid spillover of activated H species from metal NPs to Rh complex. In addition, the size-sieving effect of POP precluded the direct interaction of enzyme and Rh complex confined in the pores, enabling the success coupling of core-shell nanoreactor and aldehyde ketone reductase (AKR) for chemoenzymatic reduction of acetophenone to (R)-1-phenylethan-1-ol. This work provides a strategy for the rational manipulation of multicomponent cooperation catalysis.     

Recent Advances in Photocatalytic Oxidation of Methane to Methanol

Methane is one of the promising alternatives to non-renewable petroleum resources since it can be transformed into added-value hydrocarbon feedstocks through suitable reactions. The conversion of methane to methanol with a higher chemical value has recently attracted much attention. The selective oxidation of methane to methanol is often considered a “holy grail” reaction in catalysis. However, methanol production through the thermal catalytic process is thermodynamically and economically unfavorable due to its high energy consumption, low catalyst stability, and complex reactor maintenance. Photocatalytic technology offers great potential to carry out unfavorable reactions under mild conditions. Many in-depth studies have been carried out on the photocatalytic conversion of methane to methanol. This review will comprehensively provide recent progress in the photocatalytic oxidation of methane to methanol based on materials and engineering perspectives. Several aspects are considered, such as the type of semiconductor-based photocatalyst (tungsten, titania, zinc, etc.), structure modification of photocatalyst (doping, heterojunction, surface modification, crystal facet re-arrangement, and electron scavenger), factors affecting the reaction process (physiochemical characteristic of photocatalyst, operational condition, and reactor configuration), and briefly proposed reaction mechanism. Analysis of existing challenges and recommendations for the future development of photocatalytic technology for methane to methanol conversion is also highlighted.     

Mild,Redox-Neutral Formylation of Aryl Chlorides through the Photocatalytic Generation of Chlorine Radicals

We report a redox-neutral formylation of aryl chlorides that proceeds through selective 2-functionalization of 1,3-dioxolane through nickel and photoredox catalysis. This scalable benchtop approach provides a distinct advantage over traditional reductive carbonylation in that no carbon monoxide, pressurized gas, or stoichiometric reductant is employed. The mild conditions give unprecedented scope from abundant and complex aryl chloride starting materials.     

光催化还原二氧化碳全反应的研究进展

通过光催化将二氧化碳(CO₂)还原为可持续的绿色太阳能燃料是同时解决环境问题和能源危机的极具前景的方案.尽管迄今为止已经进行了广泛的研究,但实现高转化率、高选择性和高稳定性的光催化二氧化碳还原仍有许多障碍.如将水作为电子供体而非牺牲试剂,能够使反应的吉布斯自由能变ΔG>0,这对于真正实现理想化的人工光合作用至关重要,但同时也会为光催化还原CO₂体系带来更多的挑战.我们首先简要介绍了光催化还原CO₂的机理与挑战,而后根据目前光催化还原CO₂在无牺牲剂体系中出现的问题总结了对应的策略以及最新的研究进展,包括能带结构的调整、助催化剂的负载、异质结的构建、 MOFs与COFs材料的设计等方面,最后对目前仍未解决的问题以及未来实现工业化应用的阻碍进行了总结.     

Recent Advances in Photochemical Asymmetric Three-Component Reactions

Over the past decades, asymmetric photochemical synthesis has garnered significant attention for its sustainability and unique ability to generate enantio-enriched molecules through distinct reaction pathways. Photochemical asymmetric three-component reactions have demonstrated significant potential for the rapid construction of chiral compounds with molecular diversity and complexity. However, noteworthy challenges persist, including the participation of high-energy intermediates such as radical species, difficulties in precise control of stereoselectivity, and the presence of competing background and side reactions. Recent breakthroughs have led to the development of sophisticated strategies in this field. This review explores the intricate mechanisms, synthetic applications, and limitations of these methods. We anticipate that it will contribute towards advancing asymmetric catalysis, photochemical synthesis, and green chemistry.     

细胞内NAD(P)H水平分析技术的研究进展

细胞内NAD(P)H水平直接控制着细胞的衰老、节律、癌变、死亡等重大生命过程,NAD(P)H水平的研究是生命过程中新的研究热点之一.本文介绍了NAD(P)H的结构、特性及检测方法,重点探讨了近年来国内外NAD(P)H水平的检测,并对其研究现状进行了综述.     

Recent Advances in Photoinduced Modification of Amino Acids,Peptides, and Proteins

The chemical modification of biopolymers like peptides and proteins is a key technology to access vaccines and pharmaceuticals. Similarly, the tunable derivatization of individual amino acids is important as they are key building blocks of biomolecules, bioactive natural products, synthetic polymers, and innovative materials. The high diversity of functional groups present in amino acid-based molecules represents a significant challenge for their selective derivatization Recently, visible light-mediated transformations have emerged as a powerful strategy for achieving chemoselective biomolecule modification. This technique offers numerous advantages over other methods, including a higher selectivity, mild reaction conditions and high functional-group tolerance. This review provides an overview of the most recent methods covering the photoinduced modification for single amino acids and site-selective functionalization in peptides and proteins under mild and even biocompatible conditions. Future challenges and perspectives are discussed beyond the diverse types of photocatalytic transformations that are currently available.     

Ubiquinone‐Rhodol (UQ‐Rh) for Fluorescence Imaging of NAD(P)H through Intracellular Activation

The nicotinamide adenine dinucleotide (NAD) derivatives NADH and NADPH are critical components of cellular energy metabolism and operate as electron carriers. A novel fluorescent ubiquinone‐rhodol derivative (UQ‐Rh) was developed as a probe for NAD(P)H. By using the artificial promoter [(η⁵‐C₅Me₅)Ir(phen)(H₂O)]²⁺, intracellular activation and imaging of NAD(P)H were successfully demonstrated. In contrast to bioorthogonal chemistry, this “bioparallel chemistry” approach involves interactions with native biological processes and could potentially be used to control or investigate cellular systems.