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Inorganic Chemistry Frontiers · 2020 ·Vol. 7 ·期 20 ·4020-4027 · IF 5.958

Near-infrared phosphorescent terpyridine osmium(II) photosensitizer complexes for photodynamic and photooxidation therapy

Chen Ge,Jiayi Zhu,Ai Ouyang,Nong Lu,Yi Wang,Qianling Zhang,Pingyu Zhang

Osmium(II) complexes usually exhibit an excellent NIR (near-infrared) emission, which conforms to the optical window in a biological system. Here we designed three mitochondria-targeted NIR terpyridine Os(II) complexes as photosensitizers, which demonstrated great NIR phosphorescence emission and long phosphorescence lifetime. The emission spectra of the osmium(II) complexes were red-shifted with increasing conjugated planes of their terpyridine ligand (Os3 > Os2 > Os1). Furthermore, the Os(II) complexes, especially Os3, could produce singlet oxygen and oxidize NADH under both 465 nm and 633 nm LED light irradiation. It was found that Os3 has certain phototoxicities upon red light irradiation, and have great potential for NIR photodynamic therapy.

研究领域: 光动力疗法 · 光化学 · 无机化学 · 生物医学工程
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GREEN CHEMISTRY · 2018 ·Vol. 20 ·期 10 ·2382-2391 · IF 8.586

D-Tagatose manufacture through bio-oxidation of galactitol derived from waste xylose mother liquor

Feng Sha,Yucong Zheng,Jiao Chen,Kequan Chen,Fei Cao,Ming Yan,Pingkai Ouyang

In this study, the bio-oxidation of galactitol to the valuable D-tagatose is presented. This proposed strategy could start with the refined by-product of waste xylose mother liquor formed by chemical hydrogenation. Through a computationally guided enzyme screening approach, a robust polyol dehydrogenase (PdPDH) was rapidly identified from a massive number of candidates. When coupled with a water-forming NADH oxidase (StNOX) for environmentally benign cofactor regeneration, subsequent reaction optimization facilitated the complete transformation of 100 g L−1 galactitol into the desired product within 15 h, with a yield of 91% in a 2 L scale preparative reaction. Compared to the current enzymatic isomerization system, our approach avoids low conversion, high operative temperatures and by-product formation, while enabling simplified product isolation.

研究领域: 生物技术 · 酶学 · 可持续化学
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BIORESOURCE TECHNOLOGY · 2017 · IF 5.651

Efficient synthesis of a (S)-fluoxetine intermediate using carbonyl reductase coupled with glucose dehydrogenase

Yunping Tang,Guomei Zhang,Zheng Wang,Dan Liu,Linglu Zhang,Yafeng Zhou,Ju Huang,Fangmiao Yu,Zuisu Yang,Guofang Ding

(S)-3-chloro-1-phenyl-1-propanol ((S)-CPPO) is an important chiral intermediate predominantly used in the synthesis of the chiral side chain of (S)-fluoxetine. In this study, carbonyl reductase (CBR) from Novosphingobium aromaticivorans was successfully expressed in recombinant E. coli . The enzymatic activity of the recombinant CBR was significantly increased to 1875 U/mL in the fed-batch fermentation in a 10 L fermenter and recombinant CBR was then purified and characterized. By regenerating NADH with glucose dehydrogenase, 100 g/L 3-chloro-1-phenyl-1-propanone (3-CPP) was successfully converted to (S)-CPPO with a conversion of 100% and ee value of 99.6% after 12 h at 30 °C in PBS buffer (pH 7.0), which are the highest reported to date for the bio-production of (S)-CPPO and presented great potential for green production of (S)-CPPO at industrial scale.

研究领域: 生物技术 · 酶学 · 药物化学 · 工业生物催化
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BIORESOURCE TECHNOLOGY · 2022 · IF 11.889

The enhancement on biohydrogen production by the driving forces from extracellular iron oxide respiration

Lei Yu,Wei-xin Cheng,Quan Wang

Biohydrogen productions from xylose and glucose under dark condition were enhanced by the presence of natural Fe 3 O 4 . The electron equivalent of H 2 fractions accounted for 4.55 % and 5.69 % of the total given xylose and glucose in the experiments without Fe 3 O 4 , and that were correspondingly increased to 5.14 % and 6.50 % in the experiments with 100 mg/L of Fe 3 O 4 , respectively. Moreover, Fe 3 O 4 increased the total intracellular NAD(H) concentrations by 8.84 % and 8.37 %, and boosted the ratios of NADH/NAD + by 8.33 % and 17.72 % in xylose and glucose fermentation, respectively, comparing to the corresponding control experiments. The formation of electron couples of Fe(III)/Fe(II) during the iron oxide respiration and more generation of active extracellular polymeric substances components were determined as the important reasons for the improved biohydrogen production performance. Thus, a promotion mechanism of the internal “driving forces” from extracellular iron oxide respiration on the biohydrogen production was proposed.

CAS / MDL: 1317-61-9
研究领域: 生物技术 · 环境工程 · 微生物学
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MICROCHEMICAL JOURNAL · 2022 · IF 5.304

CuFe2O4 magnetic particles assisted construction of a label-free fluorescent sensor for detection of Escherichia coli

Li Fu,Qingmei Chen,Suqi Deng,Li Jia

An economical and label-free fluorescent sensor was developed for the selective detection of Escherichia coli ( E. coli ) based on the competitive reduction of Cu 2+ in CuFe 2 O 4 magnetic particles (MPs) by E. coli and o -phenylenediamine (OPD). Cu 2+ in CuFe 2 O 4 MPs can oxidize OPD to generate 2,3-diaminophenazine (OPDox) with fluorescent property. The presence of E. coli can weaken the oxidative ability of CuFe 2 O 4 MPs toward OPD owing to the copper reductase activity of NADH dehydrogenase-2 (NDH-2) in E. coli . NDH-2 can reduce Cu 2+ to Cu + , thereby inhibiting the OPD oxidation and resulting in the decrease of the fluorescence of the system. Under the optimum conditions, the fluorescent sensor exhibited a wide linear response to E. coli in the concentration range of 10 3 – 10 6 cfu mL −1 , and the detection limit was calculated to be 5.8 × 10 2 cfu mL −1 . Furthermore, the feasibility of the sensor was verified by successful detection of E. coli in popsicle and swimming pool water samples. More importantly, the sensor utilized the magnetic property of CuFe 2 O 4 MPs to realize the phase separation, thus averting the interference of other impurities in the sample matrix.

CAS / MDL: 7705-08-0
研究领域: 分析化学 · 生物技术 · 环境科学 · 微生物学
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MOLECULES · 2022 ·Vol. 27 ·期 18 ·6009 · IF 4.927

Synthesis of a Rare Water-Soluble Silver(II)/Porphyrin and Its Multifunctional Therapeutic Effect on Methicillin-Resistant Staphylococcus aureus

Jiaqi He,Yu Yin,Yingjie Shao,Wenkai Zhang,Yanling Lin,Xiuping Qian,Qizhi Ren

Porphyrin derivatives are popular photodynamic therapy (PDT) agents; however, their typical insolubility in water has made it challenging to separate cells of organisms in a liquid water environment. Herein, a novel water-soluble 5,10,15,20-tetrakis(4-methoxyphenyl-3-sulfonatophenyl) porphyrin (TMPPS) was synthesized with 95% yield by modifying the traditional sulfonation route. The reaction of TMPPS with AgNO3afforded AgTMPPS an unusual Ag(II) oxidation state (97% yield). The free base and Ag(II) complex were characterized by matrix-assisted laser desorption ionization-mass spectroscopy, and1H nuclear magnetic resonance, Fourier-transform infrared, UV-vis, fluorescence, and X-ray photolectron spectroscopies. Upon 460 nm laser irradiation, AgTMPPS generated a large amount of1O2, whereas no ⦁OH was detected. Antibacterial experiments on methicillin-resistantStaphylococcus aureus(MRSA) revealed that the combined action of AgⅡions and PDT could endow AgTMPPS with a 100% bactericidal ratio for highly concentrated MRSA (108CFU/mL) at a very low dosage (4 μM) under laser irradiation at 360 J/cm2. Another PDT response was demonstrated by photocatalytically oxidizing 1,4-dihydronicotinamide adenine dinucleotide to NAD+with AgTMPPS. The structural features of the TMPPS and AgTMPPS molecules were investigated by density functional theory quantum chemical calculations to demonstrate the efficient chemical and photodynamical effects of AgTMPPS for non-invasive antibacterial therapy.Keywords:bivalent silver complex;sulfonated porphyrin;photodynamic therapy;photocatalytic NADH oxidation;multifunctional effect;methicillin-resistantStaphylococcus aureus

研究领域: 生物化学 · 微生物学 · 药物化学
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Science China-Chemistry · 2025 · IF 9.7

Far-red-excitable ultra-long-lived organic photocatalyst for photocatalytic decaging

Li Ying-Ze,Lin Wen-Yue,Li Jia-Yao,Zhang Zhi-Zhuo,Gao Qing-Hua,Zhang Ming-Yu,Jiang Lin-Han,Guo Dong-Xue,Peng Yi,Feng Hong-Juan,Huang Zhi,Jia Chuan-Cheng,Huang Ling

Photomodulation technology, characterized by its high spatiotemporal resolution, has emerged as a transformative approach for precise, rapid, and noninvasive regulation of intricate cellular signaling networks, offering unprecedented opportunities for biomedical research. Nevertheless, the in vivo implementation of wireless photomodulation remains constrained by the inherent limitations of conventional photoresponsive systems. Addressing this challenge, we report a BODIPY-based photocatalyst with exceptional red-light responsiveness ( λ > 630 nm). Transient spectroscopic studies show that this photocatalyst exhibits the feature with solvent polarity-switching excited state dynamics. In addition, we observed ultralong triplet-state lifetimes (590 µs in tetrahydrofuran; 862 µs in toluene), which is favorable for establishing a far-red-light-driven photocatalytic decaging platform that synergistically integrates the BODIPY photocatalyst with endogenous NADH as the intrinsic electron donor. Crucially, this system demonstrates robust in vivo efficacy, achieving significant tumor growth suppression in murine tumor models through localized prodrug activation. This work not only provides fundamental insights into engineering long-lived triplet states in metal-free organic photocatalysts but also pioneers a biocompatible strategy for spatiotemporally controlled therapeutic interventions, bridging the gap between advanced photochemistry and precision biomedicine.

研究领域: 光化学 · 肿瘤学 · 分子医学 · 生物材料 · 药物递送 · 转化医学 · 光动力治疗
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Small · 2024 · IF 13

Piezoelectric Catalysis Induces Tumor Cell Senescence to Boost Chemo-Immunotherapy

Zining Hao,Shu Guo,Wenkang Tu,Qiang Wang,Jing Wang,Xuwu Zhang,Yuchu He,Dawei Gao

Cellular senescence, a vulnerable state of growth arrest, has been regarded as a potential strategy to weaken the resistance of tumor cells, leading to dramatic improvements in treatment efficacy. However, a selective and efficient strategy for inducing local tumor cellular senescence has not yet been reported. Herein, piezoelectric catalysis is utilized to reduce intracellular NAD + to NADH for local tumor cell senescence for the first time. In detail, a biocompatible nanomedicine (BTO/Rh-D@M) is constructed by wrapping the piezoelectric BaTiO 3 /(Cp * RhCl 2 ) 2 (BTO/Rh) and doxorubicin (DOX) in the homologous cytomembrane with tumor target. After tumors are stimulated by ultrasound, negative and positive charges are generated on the BTO/Rh by piezoelectric catalysis, which reduce the intracellular NAD + to NADH for cellular senescence and oxidize H 2 O to reactive oxygen species (ROS) for mitochondrial damage. Thus, the therapeutic efficacy of tumor immunogenic cell death-induced chemo-immunotherapy is boosted by combining cellular senescence, DOX, and ROS. The results indicate that 23.9% of the piezoelectric catalysis-treated tumor cells senesced, and solid tumors in mice disappeared completely after therapy. Collectively, this study highlights a novel strategy to realize cellular senescence utilizing piezoelectric catalysis and the significance of inducing tumor cellular senescence to improve therapeutic efficacy.

研究领域: 生物医学工程 · 肿瘤学 · 纳米技术 · 免疫疗法
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Small · 2022 ·Vol. 19 ·期 13 ·2201305 · IF 15.153

Light-Harvesting Artificial Cells Containing Cyanobacteria for CO2 Fixation and Further Metabolism Mimicking

Boyu Yang,Shubin Li,Wei Mu,Zhao Wang,Xiaojun Han

The bottom-up constructed artificial cells help to understand the cell working mechanism and provide the evolution clues for organisms. The energy supply and metabolism mimicry are the key issues in the field of artificial cells. Herein, an artificial cell containing cyanobacteria capable of light harvesting and carbon dioxide fixation is demonstrated to produce glucose molecules by converting light energy into chemical energy. Two downstream “metabolic” pathways starting from glucose molecules are investigated. One involves enzyme cascade reaction to produce H 2 O 2 (assisted by glucose oxidase) first, followed by converting Amplex red to resorufin (assisted by horseradish peroxidase). The other pathway is more biologically relevant. Glucose molecules are dehydrogenated to transfer hydrogens to nicotinamide adenine dinucleotide (NAD + ) for the production of nicotinamide adenine dinucleotide hydride (NADH) molecules in the presence of glucose dehydrogenase. Further, NADH molecules are oxidized into NAD + by pyruvate catalyzed by lactate dehydrogenase, meanwhile, lactate is obtained. Therefore, the cascade cycling of NADH/NAD + is built. The artificial cells built here pave the way for investigating more complicated energy-supplied metabolism inside artificial cells.

CAS / MDL: 7758-99-8 127-17-3
研究领域: 生物技术 · 生物化学 · 合成生物学 · 细胞工程
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

A dual-enzyme microreactor based on encapsulation and covalent bond for enzymatic electrocatalytic CO2 reduction

Guanhua Liu,Lirong Wang,Lihang Yan,Hao Zhao,Yaoxuan Li,Liya Zhou,Ying He,Li Ma,Yunting Liu,Jing Gao,Yanjun Jiang

Enzymatic reduction of CO 2 into high-value chemicals has become an emerging technology attributed to its high selectivity and catalytic efficiency under mild conditions. While, the low solubility of CO 2 at room temperature, the expensive cofactors and the poor stability of free enzyme limit the application potential. To solve these problems, we used organic microcapsules together with MOF to protect formate dehydrogenase (FDH) by encapsulation and carbonic anhydrase (CA) by covalent bond with high CO 2 capture ability to construct a dual-enzyme microreactor. Besides, the additional mesopores of the microreactor can ensure the efficient internal diffusion of the substrate and product. Electron mediator was used to enhance electrocatalytic NADH regeneration to efficiently reduce CO 2 to formate in the enzyme electrocatalysis system. After optimization, the highest yield of formate in the electrocatalytic CO 2 reduction system by the dual enzyme microreactor was 2.917 mM with a generation rate of 1.296 × 10 4 μmol g cat -1 h −1 , which was 8.9 times higher than free enzyme.

研究领域: 化学工程 · 生物催化 · 电化学 · 环境科学
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JOURNAL OF CATALYSIS · 2023 · IF 7.3

Dual-core drive hydrogen transfer heterogeneous catalysts based on iridium-enzyme co-modified carbon nanotubes for aromatic aldehyde hydrogenation

Li-Jun Zhao,Caimei Zhang,Shixin Zhang,Jiayang Chen,Xiaoyi Lv,Huijuan Su,Xun Sun,Toru Murayama,Caixia Qi

Here, a novel dual-core drive transfer hydrogen heterogeneous catalysts Ir@CNT@ADH were developed by sequentially immobilizing the NADH-dependent alcohol dehydrogenase ADH and high active NADH-regenerated catalyst Pyren-Ir1 on the surface of carbon nanotubes. Two pyrene-functionalized Ir-complex, Pyrene-Ir1 and Pyrene-Ir2 , were synthesized and demonstrated exceptional coenzyme NADH generation performances, ensuring continuous in situ NADH generation in the enzyme-catalyzed process . These complexes could be easily modified onto carbon nanotube materials by mild π-π conjugated adsorption. The catalysts Ir@CNT@ADH showed significantly improved catalytic hydrogenation efficiency in the reduction of benzaldehyde to the corresponding alcohol, compared to the single Pyrene-Ir1 modified carbon nanotube catalyst Ir@CNT and homogeneous catalytic system in the presence of a catalytic amount of NAD + . The yield of benzyl alcohol increased by more than 50 % in all cases. We assume that the designed dual-core drive heterogeneous catalyst strategy could effectively address the mutual inactivation problem of enzyme and Iridium complexes by blocking the contact between enzymes with Iridium complexes and enhancing the in situ regeneration property of coenzyme NADH in the enzyme catalytic system. Furthermore, catalyst Ir@CNT@ADH also demonstrated excellent catalytic hydrogeneration performances for various substituted benzaldehyde with good recycling performance. Therefore, the proposed dual-core drive heterogeneous catalyst strategy holds great potential for the combined industrial application of chemical catalysts and bioenzymes. It is expected to contribute to the development and preparation of higher-value biochemical products.

研究领域: 催化 · 化学工程 · 生物化学 · 材料科学
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SHOCK · 2024 · IF 2.7

D4-Chip Reveals Impaired T Cell Function in Sepsis: Insights from Plasma Microenvironment Analysis and Mitochondrial Targeted Therapy

Liu Lijuan,Wang Ruoyu,Pu Xuexue,Zha Yutao,Yang Xiao,Fang Xiao,Liu Yong,Shao Min,Zhu Ling,Ren Xiaoou,Deng Guoqing,Yang Ke

Background Sepsis, a systemic inflammation syndrome initiated by infection, poses significant challenges due to its intricate pathophysiology. T cells play a crucial role in combating infections during sepsis. Despite previous observations indicating T cell dysfunction in sepsis, reliable in-vitro detection methods were lacking, and the factors influencing these impairments remained unclear. Methods We developed a novel method using the D 4 -Chip to assess sepsis T cell migration function. This microfluidic platform enabled precise analysis of migration function under controlled conditions. Additionally, We explored the impact of the plasma microenvironment on T cell behavior, along with the redox environment in sepsis, and assessed the potential efficacy of Mitoquinone mesylate (MitoQ), a mitochondrial-targeted drug. Results Our findings revealed impaired migration function in sepsis T cells compared to healthy controls. Interestingly, sepsis plasma enhanced the migration of healthy T cells, yet incubation with healthy plasma did not fully restore migration impairments in sepsis T cells. Subsequent investigations uncovered a significant increase in NADH/NAD+ levels in sepsis T cells, with healthy T cells exposed to various sepsis plasma conditions also showing elevated NADH/NAD+ levels. Importantly, MitoQ normalized abnormal intracellular NADH/NAD+ levels and enhanced the migration ability of T cells. Conclusions Short-term incubation with sepsis plasma does not directly inhibit T cell migration but instead affects T cell function by disrupting the intracellular redox environment. Improving the intracellular redox environment of sepsis patients contributes to restoring impaired migration and proliferation, with MitoQ demonstrating therapeutic potential.

研究领域: 免疫学 · 传染病学 · 药理学 · 细胞生物学
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