porphyrin

卟啉
  • 文章类型: Case Reports
    该病例报告描述了一名28岁的红细胞生成卟啉症(EPP)患者。在接受静脉铁输注后,他的病情严重恶化。病人面部和手臂出现水疱皮疹,除恶心外,还有严重的瘙痒和灼烧感,呕吐,和黑色的呕吐物.实验室检查发现肝功能异常和贫血。皮肤科的快速诊断和多学科护理,胃肠,血液学专家是必不可少的。严格避光,症状管理技术,和停止静脉铁是治疗计划的一部分。患者的症状在12个月内消退,他恢复了他的正常活动。在管理EPP时,关键学习点强调了警惕性在发现触发变量方面的重要性,及时诊断,避光,一致的后续行动,和遗传咨询。
    This case report describes a 28-year-old man with erythropoietic porphyria (EPP). After receiving an intravenous iron infusion, he experienced a significant acute aggravation of his condition. The patient had a vesicular rash on the face and arms with severe itching and burning feelings in addition to nausea, vomiting, and black-colored vomit. Abnormal liver function tests and anemia were found in the lab tests. Quick diagnosis and multidisciplinary care from dermatology, gastrointestinal, and hematology experts were essential. Strict light avoidance, symptom management techniques, and cessation of intravenous iron were all part of the treatment plan. The patient\'s symptoms subsided over a period of 12 months, and he resumed his regular activities. In managing EPP, key learning points stress the importance of vigilance in spotting trigger variables, prompt diagnosis, light avoidance, consistent follow-up, and genetic counseling.
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  • 文章类型: Journal Article
    基于卟啉的多孔有机聚合物由于其在氧气活化方面的优越性而被广泛用于可见光下的光催化氧化。相比之下,效率通常是有限的,由于快速复合和缓慢的电子转移。在这里,我们报道了使用基于三卟啉的共价三嗪骨架(Por-CTF)作为可见光活性光催化剂,用于在室温下将胺氧化偶联为亚胺。通过掺入π共轭卟啉结构单元导致分子之间电子传输增强,以及激发电子的复合时间延长。Por-CTF的光催化效率优于没有三嗪骨架的聚合物(POP-TSP),以四-(4-乙烯基苯基)卟啉为单体通过自由基聚合制备。Por-CTF催化剂对各种伯胺具有优异的效率和稳定性。该工作为提高光催化氧化效率提供了合理的催化剂分子结构设计指导。
    Porphyrins-based porous organic polymers were widely used in photocatalytic oxidation under visible light owing to their superiority in the activation of oxygen. In contrast, the efficiency is usually limited due to the fast recombination and slow electron transfer. Herein, we report the use of a trioporphyrins-based covalent triazine framework (Por-CTF) as visible-light-active photocatalyst for the coupling oxidative of amines to imines at room temperature. By incorporating the π-conjugated porphyrin building block led to the enhanced electron transport between molecules, and the extended recombination time of excited electrons. The photocatalytic efficiency of Por-CTF is superior to that of polymer in absence of triazine framework (POP-TSP), which was prepared by radical polymerization using tetra-(4-vinylphenyl) porphyrin as monomer. Por-CTF catalyst presented excellent efficiency for various primary amines and stability. This work provides a reasonable guidance of catalyst molecular structure design for enhancing efficiency in the photocatalytic oxidation.
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  • 文章类型: Journal Article
    模拟自然光能系统的光活性人造纳米催化剂可以产生清洁和可再生能源。然而,它们的光吸收能力差和不受欢迎的光生电子-空穴复合阻碍了它们的生产。在这里,我们通过将内消旋四(对羟基苯基)卟啉光敏剂的定制自组装与二氧化钛(TiO2)的生长相结合,设计了两种具有不同微观结构的纳米催化剂。卟啉光吸收天线有效地扩展了TiO2在可见光区的吸收范围,锐钛矿型TiO2促进了卟啉电子-空穴的高效分离。光诱导的电子被转移到Pt助催化剂的表面,用于通过水分解产生氢,并利用该空穴分解甲基橙染料。由于大量的活性位点和增加的光生电子输出,与核@壳结构相比,混合结构显示出大大提高的光催化性能。这种受控的装配调节为制造先进的,结构依赖的光催化剂。
    Photoactive artificial nanocatalysts that mimic natural photoenergy systems can yield clean and renewable energy. However, their poor photoabsorption capability and disfavored photogenic electron-hole recombination hinder their production. Herein, we designed two nanocatalysts with various microstructures by combining the tailored self-assembly of the meso-tetra(p-hydroxyphenyl) porphine photosensitizer with the growth of titanium dioxide (TiO2). The porphyrin photoabsorption antenna efficiently extended the absorption range of TiO2 in the visible region, while anatase TiO2 promoted the efficient electron-hole separation of porphyrin. The photo-induced electrons were transferred to the surface of the Pt co-catalyst for the generation of hydrogen via water splitting, and the hole was utilized for the decomposition of methyl orange dye. The hybrid structure showed greatly increased photocatalytic performance compared to the core@shell structure due to massive active sites and increased photo-generated electron output. This controlled assembly regulation provides a new approach for the fabrication of advanced, structure-dependent photocatalysts.
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  • 文章类型: Journal Article
    肝脏,人体新陈代谢的关键器官,作为血红素生物合成的主要场所,骨髓旁边.在健康的肝脏中,保持对血红素生产的精确控制是最重要的,以满足高代谢需求,同时避免中间代谢物的潜在毒性。特别是原卟啉IX。有趣的是,我们最近的研究揭示了一种被破坏的血红素生物合成过程,称为“卟啉过度驱动”,在癌症中促进血红素中间体的积累,可能支持肿瘤的生存。这里,我们调查血红素和卟啉代谢在健康和致癌的人类肝脏,利用原发性人类肝脏转录组学和单细胞RNA测序(scRNAseq)。我们的研究揭示了健康肝脏血红素生物合成中稳健的基因表达模式,支持电子传递链(ETC)和细胞色素P450功能没有中间积累。相反,肝癌表现出重排血红素生物合成和细胞色素P450基因表达的大量下调。值得注意的是,尽管药物代谢减少,基因表达分析显示,血红素供应到ETC保持很大程度上不变,甚至随着患者癌症进展而升高,建议代谢优先转移。肝癌选择性地积累中间体,在正常组织中不存在,通过表达分析推断它们在疾病进展中的作用。此外,我们在基因组学中的发现建立了卟啉代谢的异常基因表达与侵袭性癌症中较差的总体生存率之间的联系,指示临床治疗开发的潜在目标。我们提供了关于通过药物协同策略靶向卟啉超速的体外概念验证数据。
    The liver, a pivotal organ in human metabolism, serves as a primary site for heme biosynthesis, alongside bone marrow. Maintaining precise control over heme production is paramount in healthy livers to meet high metabolic demands while averting potential toxicity from intermediate metabolites, notably protoporphyrin IX. Intriguingly, our recent research uncovers a disrupted heme biosynthesis process termed \'porphyrin overdrive\' in cancers that fosters the accumulation of heme intermediates, potentially bolstering tumor survival. Here, we investigate heme and porphyrin metabolism in both healthy and oncogenic human livers, utilizing primary human liver transcriptomics and single-cell RNA sequencing (scRNAseq). Our investigations unveil robust gene expression patterns in heme biosynthesis in healthy livers, supporting electron transport chain (ETC) and cytochrome P450 function without intermediate accumulation. Conversely, liver cancers exhibit rewired heme biosynthesis and a massive downregulation of cytochrome P450 gene expression. Notably, despite diminished drug metabolism, gene expression analysis shows that heme supply to the ETC remains largely unaltered or even elevated with patient cancer progression, suggesting a metabolic priority shift. Liver cancers selectively accumulate intermediates, which are absent in normal tissues, implicating their role in disease advancement as inferred by expression analysis. Furthermore, our findings in genomics establish a link between the aberrant gene expression of porphyrin metabolism and inferior overall survival in aggressive cancers, indicating potential targets for clinical therapy development. We provide in vitro proof-of-concept data on targeting porphyrin overdrive with a drug synergy strategy.
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  • 文章类型: Journal Article
    这项研究研究了通过C-H活化采用氧化O环化方法合成四-和八-O-融合卟啉类。尽管在常规解决方案中遇到诸如过氧化和不稳定性等挑战,在超高真空(UHV)条件下,在Au(111)表面上成功合成。X射线光电子能谱,扫描隧道显微镜,和非接触式原子力显微镜阐明了吡喃部分通过C-O键形成和随后的由C-H*O相互作用驱动的自组装的优先形成。此外,发现O-环化过程通过提升HOMO能级来减少HOMO-LUMO间隙,随着嵌入O原子数量的增加,效果也会上升。
    This study investigates the synthesis of tetra- and octa-O-fused porphyrinoids employing an oxidative O-annulation approach through C-H activation. Despite encountering challenges such as overoxidation and instability in conventional solution protocols, successful synthesis was achieved on Au(111) surfaces under ultra-high vacuum (UHV) conditions. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and non-contact atomic force microscopy elucidated the preferential formation of pyran moieties via C-O bond formation and subsequent self-assembly driven by C-H∙∙∙O interactions. Furthermore, the O-annulation process was found to reduce the HOMO-LUMO gap by lifting the HOMO energy level, with the effect rising upon increasing the number of embedded O-atoms.
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  • 文章类型: Journal Article
    电子供体和电子受体(D/A)之间的相互作用对有机太阳能电池(OSC)的性能起着重要作用。虽然已知异构化策略可以优化分子的几何形状和性质,异构化对D/A相互作用中供体或受体的影响尚未得到广泛研究。在这里,我们通过在苯基的间位和对位连接两个官能化的卟啉来合成两个小分子供体m-ph-ZnP2和p-ph-ZnP2,创新性地研究了供体异构对D/A相互作用的影响。分别。与p-ph-ZnP2相比,m-ph-ZnP2显示出减少的自聚集,但与PC61BM相比。因此,与PCE为2.03%的p-ph-ZnP2器件相比,m-ph-ZnP2二元OSC实现了5.43%的高得多的功率转换效率(PCE)。基于m-ph-ZnP2的器件的性能增强主要归因于更强的分子内电荷转移(ICT),增强的D/A交互,改进的电荷转移,和抑制的电荷重组。此外,基于m-ph-ZnP2:Y6:PC61BM的三元器件实现8.34%的PCE。总之,这项工作阐明了化学结构之间的关系,D/A交互和设备性能,为设计有效的OSC材料提供有价值的指导。
    The interactions between the electron donors and electron acceptors (D/A) play important roles for the performance of organic solar cells (OSCs). While the isomerization strategy is known to optimize molecular geometries and properties, the impacts of isomerization on the donors or acceptors in D/A interactions have not been extensively investigated. Here in, we innovatively investigated the impacts of donor isomerism on the D/A interactions by synthesizing two small molecule donors m-ph-ZnP2 and p-ph-ZnP2 by linking two functionalized porphyrins at the meta and para positions of phenyl groups, respectively. Compared with p-ph-ZnP2, m-ph-ZnP2 displays reduced self-aggregation but  with PC61BM. Consequently, a much higher power conversion efficiency (PCE) of 5.43% is achieved for the m-ph-ZnP2 binary OSCs than the p-ph-ZnP2 devices with a PCE of 2.03%. The enhanced performance of m-ph-ZnP2-based device can be primarily attributed to the stronger intramolecular charge transfer (ICT), the enhanced D/A interactions, the improved charge transfer, and the suppressed charge recombination. Furthermore, the ternary devices based on m-ph-ZnP2:Y6:PC61BM achieve a PCE of 8.34%. In short, this work elucidates the relationship among the chemical structure, D/A interactions and device performance, providing valuable guidelines for designing efficient OSCs materials.
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  • 文章类型: Journal Article
    光动力疗法(PDT)在癌症治疗中引起了极大的关注,而其治疗效果受到不令人满意的光敏剂和缺氧肿瘤微环境(TME)的限制。为了解决这些问题,我们已经开发了过氧化氢酶负载的锰-卟啉框架(CAT@MnPFs)用于癌细胞的催化辅助PDT。通过将Mn2离子和PpIX组装成MnPFs并随后加载过氧化氢酶来构建CAT@MnPFs。在650nm的光照射下,CAT@MnPFs结构中的卟啉(原卟啉IX)可以将氧(O2)转化为单线态氧(1O2),显示光动力效果。重要的是,负载的过氧化氢酶可以在600s内将过氧化氢(H2O2)分解为O2,O2水平大幅升高(13.22mgL-1),从而促进通过PDT产生1O2。因此,CAT@MnPFs结合650nm的光可以有效地消融癌细胞,由于过氧化氢酶辅助的氧释放PDT,显示出较高的治疗效果。同时,与CAT@MnPFs孵育后,在正常和红细胞中可以发现不明显的损伤。因此,获得的CAT@MnPFs整合了光敏剂和过氧化氢酶用于放氧PDT的优势,这可以为治疗缺氧细胞提供一些见解。
    Photodynamic therapy (PDT) is attracting great attention for cancer treatments, while its therapeutic efficacy is limited by unsatisfactory photosensitizers and hypoxic tumor microenvironment (TME). To address these problems, we have developed catalase-loaded manganese-porphyrin frameworks (CAT@MnPFs) for catalytically-assisted PDT of cancer cells. CAT@MnPFs were constructed by the assembly of Mn2+ ions and PpIX into MnPFs and the subsequent loading of catalase. Under 650 nm light irradiation, the porphyrin (Protoporphyrin IX) within the structure of CAT@MnPFs can convert oxygen (O2) into singlet oxygen (1O2), showing the photodynamic effect. Importantly, the loaded catalase can decompose hydrogen peroxide (H2O2) into O2 with a huge elevation of O2 level (13.22 mg L-1) in 600 s, thus promoting 1O2 generation via PDT. As a result, CAT@MnPFs combined with 650 nm light can effectively ablate cancer cells due to the catalase-assisted oxygen-evolving PDT, showing a high therapeutic efficacy. Meanwhile, after the incubation with CAT@MnPFs, unobvious damage can be found in normal and red blood cells. Thus, the obtained CAT@MnPFs integrate the advantage of photosensitizers and catalase for oxygen-evolving PDT, which can provide some insight for treating hypoxic cells.
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  • 文章类型: Journal Article
    Heme,含铁的四吡咯,在几乎所有生物体中都是必不可少的。血红素生物合成需要精确调节,特别是考虑到原卟啉IX的潜在细胞毒性,血红素形成之前的中间。这里,我们报道了卟啉中间体在肿瘤微环境(TME)中的积累,我们认为这是血红素生物合成失调的结果,伴随着对中期基因的癌症生存依赖性增强,我们最近称之为“卟啉Overdrive”的过程。具体来说,卟啉在TME的肺癌细胞和基质细胞中积累。在TME的基质细胞内,有证据支持癌症相关成纤维细胞(CAFs)通过不平衡途径积极产生卟啉.相反,正常组织没有卟啉积累,被剥夺肿瘤的CAF停止卟啉过量生产,这表明癌症和肿瘤基质卟啉过度产生都局限于癌症特异性组织生态位。我们的发现的临床相关性是通过建立不平衡的卟啉产生与更具侵袭性的癌症的总体较差生存率之间的相关性来暗示的。这些发现阐明了特别是在肿瘤微环境中的异常卟啉动力学,提示治疗干预的潜在目标。
    Heme, an iron-containing tetrapyrrole, is essential in almost all organisms. Heme biosynthesis needs to be precisely regulated particularly given the potential cytotoxicity of protoporphyrin IX, the intermediate preceding heme formation. Here, we report on the porphyrin intermediate accumulation within the tumor microenvironment (TME), which we propose to result from dysregulation of heme biosynthesis concomitant with an enhanced cancer survival dependence on mid-step genes, a process we recently termed \"Porphyrin Overdrive\". Specifically, porphyrins build up in both lung cancer cells and stromal cells in the TME. Within the TME\'s stromal cells, evidence supports cancer-associated fibroblasts (CAFs) actively producing porphyrins through an imbalanced pathway. Conversely, normal tissues exhibit no porphyrin accumulation, and CAFs deprived of tumor cease porphyrin overproduction, indicating that both cancer and tumor-stromal porphyrin overproduction is confined to the cancer-specific tissue niche. The clinical relevance of our findings is implied by establishing a correlation between imbalanced porphyrin production and overall poorer survival in more aggressive cancers. These findings illuminate the anomalous porphyrin dynamics specifically within the tumor microenvironment, suggesting a potential target for therapeutic intervention.
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  • 文章类型: Journal Article
    重金属是最危险的水污染物,带来严重的健康和环境后果。其中,已知汞(Hg2+)离子在人类和水生生物中引起有害的健康问题。由于这个原因,已经设计了几种分析技术来检测和量化这种离子的量。然而,其中大多数需要先进的仪器,分析时间延长,和样品制备。在这项研究中,通过使用恶唑啉聚合物作为共价粘合剂将卟啉接枝到聚(对苯二甲酸乙二醇酯)片材上,开发了一种低成本且高度可重复使用的比色探针。暴露于溶液中的痕量Hg2+时,通过络合机制,制造的材料在视觉上从淡褐色粉红色过渡到绿色。此外,该探针的透明性允许定量分光光度法测定水性样品中的Hg2浓度。还表明该材料高度稳定,可以重复使用50次以上,而性能不会显着下降,因此,使其适用于不同水体中汞离子污染的现场监测。
    Heavy metals are the most hazardous water pollutants, with severe health and environmental consequences. Among these, mercuric (Hg2+) ions are known to cause detrimental health issues in both humans and aquatic life. Due to this, several analytical techniques have been devised to detect and quantify the amount of this ion. However, most of these require advanced instrumentation, prolonged analysis time, and sample preparation. In this study, a low-cost and highly reusable colorimetric probe was developed by grafting porphyrin to poly(ethylene terephthalate) sheets using an oxazoline polymer as covalent adhesive. Upon exposure to trace amounts of Hg2+ in solution, the fabricated material visually transitioned from faint brownish pink to green by the complexation mechanism. Additionally, the transparency of this probe allowed the quantitative spectrophotometric determination of the Hg2+ concentration in aqueous samples. It was also shown that the material is highly stable, which can be reused for more than 50 times without significant decline in its performance, hence, making it suitable for the onsite monitoring of mercuric ion contamination in different bodies of water.
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  • 文章类型: Journal Article
    脑胶质瘤的特点是高侵袭性,术后复发率高,高发病率和死亡率,对临床治疗提出了极大的挑战。传统治疗包括手术,放疗和化疗;它们也有显著的相关副作用,导致肿瘤切除和复发的困难。光动力疗法已被证明是帮助治疗脑恶性肿瘤的有希望的新策略。它以特定波长照射肿瘤部位以激活光敏剂,选择性地积累在肿瘤部位,引发光化学反应破坏肿瘤细胞.它具有微创的优点,针对性强,不良反应少,并有望很好地用于抗肿瘤治疗。然而,传统PDT的治疗效果受到光敏剂微弱的组织渗透能力的限制,肿瘤微环境中的缺氧和免疫抑制。本文综述了光动力疗法治疗脑胶质瘤的原理及肿瘤细胞损伤机制的研究现状,并分析了目前在胶质瘤治疗中应用的优缺点,理清了提高光敏剂组织渗透能力的分析思路。旨在为脑胶质瘤光动力疗法的改进提供可行的方向,为临床深部脑肿瘤的治疗提供参考。
    Gliomas of the brain are characterised by high aggressiveness, high postoperative recurrence rate, high morbidity and mortality, posing a great challenge to clinical treatment. Traditional treatments include surgery, radiotherapy and chemotherapy; they also have significant associated side effects, leading to difficulties in tumour resection and recurrence. Photodynamic therapy has been shown to be a promising new strategy to help treat malignant tumours of the brain. It irradiates the tumour site at a specific wavelength to activate a photosensitiser, which selectively accumulates at the tumour site, triggering a photochemical reaction that destroys the tumour cells. It has the advantages of being minimally invasive, highly targeted and with few adverse reactions, and is expected to be well used in anti-tumour therapy. However, the therapeutic effect of traditional PDT is limited by the weak tissue penetration ability of photosensitiser, hypoxia and immunosuppression in the tumour microenvironment. This paper reviews the current research status on the therapeutic principle of photodynamic therapy in glioma and the mechanism of tumour cell injury, and also analyses the advantages and disadvantages of the current application in glioma treatment, and clarifies the analysis of ideas to improve the tissue penetration ability of photosensitizers. It aims to provide a feasible direction for the improvement of photodynamic therapy for glioma and a reference for the clinical treatment of deep brain tumours.
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