photosensitization

光敏化
  • 文章类型: Journal Article
    挥发性化学产品(VCP)越来越被认为是城市大气中挥发性有机化合物(VOCs)的重要来源,可能是二次有机气溶胶(SOA)形成的关键前体。这项研究调查了VCP衍生的SOA的形成和物理化学转化,通过臭氧分解从具有代表性的房间除臭剂空气清新剂中蒸发的挥发性有机化合物产生,关注气溶胶蒸发对其分子组成的影响,光吸收性能,和活性氧(ROS)的产生。气溶胶蒸发后,溶质变得浓缩,加速气溶胶基质内的反应,导致过氧化物含量减少42%,SOA明显褐变。这个过程在中等相对湿度(~40%)下最有效,在气溶胶固化前达到最大溶质浓度。分子表征表明,蒸发VCP衍生的SOA会从现有或转化的羰基化合物与还原的氮物种之间的相互作用中产生高度共轭的含氮产物,可能作为发色团负责观察到的棕色着色。此外,通过二氧化硫(SO2)的非均相氧化阐明了VCP衍生的SOA的反应性,这表明干燥后光敏硫酸盐的产生增强。ROS的直接测量,包括单线态氧(1O2),超氧化物(O2·-),和羟基(·OH),在光照下,干燥的SOA样品与未干燥的SOA样品的丰度更高。我们的发现强调,干燥会显著改变VCP衍生的SOA的物理化学性质,影响它们在大气化学和辐射平衡中的作用。
    Volatile chemical products (VCPs) are increasingly recognized as significant sources of volatile organic compounds (VOCs) in urban atmospheres, potentially serving as key precursors for secondary organic aerosol (SOA) formation. This study investigates the formation and physicochemical transformations of VCP-derived SOA, produced through ozonolysis of VOCs evaporated from a representative room deodorant air freshener, focusing on the effects of aerosol evaporation on its molecular composition, light absorption properties, and reactive oxygen species (ROS) generation. Following aerosol evaporation, solutes become concentrated, accelerating reactions within the aerosol matrix that lead to a 42% reduction in peroxide content and noticeable browning of the SOA. This process occurs most effectively at moderate relative humidity (∼40%), reaching a maximum solute concentration before aerosol solidification. Molecular characterization reveals that evaporating VCP-derived SOA produces highly conjugated nitrogen-containing products from interactions between existing or transformed carbonyl compounds and reduced nitrogen species, likely acting as chromophores responsible for the observed brownish coloration. Additionally, the reactivity of VCP-derived SOA was elucidated through heterogeneous oxidation of sulfur dioxide (SO2), which revealed enhanced photosensitized sulfate production upon drying. Direct measurements of ROS, including singlet oxygen (1O2), superoxide (O2•-), and hydroxyl radicals (•OH), showed higher abundances in dried versus undried SOA samples under light exposure. Our findings underscore that drying significantly alters the physicochemical properties of VCP-derived SOA, impacting their roles in atmospheric chemistry and radiative balance.
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  • 文章类型: Journal Article
    芳香族羰基化合物主要被用作水性二次有机气溶胶(aqSOA)和光吸收有机气溶胶的光敏剂(即,棕色碳或BrC)形成,但是由于它们的有机性质,它们还可以经历氧化以形成aqSOA和BrC。然而,芳香羰基光敏剂的光化学转化,特别是在多组分系统中,研究不足。这项研究探索了在云/雾条件下,混合和单一系统中芳族羰基光敏剂辐照的aqSOA形成。仅由酚醛羰基组成的混合系统(VLActSyrSyrAld:香兰素[VL]乙酰丁香酮[ActSyr]丁香醛[SyrAld])和另一个由非酚醛和酚醛羰基组成的系统(DMBActSyrSyrAld:3,4-二甲氧基苯甲醛[DMB],一种非酚羰基,+ActSyr+SyrAld)与VL(VL*)和DMB(DMB*)的单一系统进行比较,分别。在混合系统中,VL和DMB的较短寿命表明它们触发其他有机化合物氧化的能力减弱(例如,愈创木酚[GUA],非羰基苯酚)。与DMB*的缓慢衰减和最小的光增强相反,VL*的快速光降解和显着的光增强表明有效的直接光敏化氧化(即,自我光敏化)。相对于单一系统,氧化剂可用性的增加促进了VLActSyrSyrAld中的功能化,并加速了DMBActSyrSyrAld中早期aqSOA的转化。此外,可氧化底物的可用性增加与更强的氧化能力相反,限制了混合系统对aqSOA光吸收的贡献。这表明来自混合光敏剂系统的BrC的辐射效应比来自单一光敏剂系统的BrC更弱。此外,随着反应系统复杂性的增加,观察到更多的氧化和氧化的aqSOA(例如,VL* Aromatic carbonyls have been mainly probed as photosensitizers for aqueous secondary organic aerosol (aqSOA) and light-absorbing organic aerosol (i.e., brown carbon or BrC) formation, but due to their organic nature, they can also undergo oxidation to form aqSOA and BrC. However, photochemical transformations of aromatic carbonyl photosensitizers, particularly in multicomponent systems, are understudied. This study explored aqSOA formation from the irradiation of aromatic carbonyl photosensitizers in mixed and single systems under cloud/fog conditions. Mixed systems consisting of phenolic carbonyls only (VL + ActSyr + SyrAld: vanillin [VL] + acetosyringone [ActSyr] + syringaldehyde [SyrAld]) and another composed of both nonphenolic and phenolic carbonyls (DMB + ActSyr + SyrAld: 3,4-dimethoxybenzaldehyde [DMB], a nonphenolic carbonyl, + ActSyr + SyrAld) were compared to single systems of VL (VL*) and DMB (DMB*), respectively. In mixed systems, the shorter lifetimes of VL and DMB indicate their diminished capacity to trigger the oxidation of other organic compounds (e.g., guaiacol [GUA], a noncarbonyl phenol). In contrast to the slow decay and minimal photoenhancement for DMB*, the rapid photodegradation and significant photoenhancement for VL* indicate efficient direct photosensitized oxidation (i.e., self-photosensitization). Relative to single systems, the increased oxidant availability promoted functionalization in VL + ActSyr + SyrAld and accelerated the conversion of early generation aqSOA in DMB + ActSyr + SyrAld. Moreover, the increased availability of oxidizable substrates countered by stronger oxidative capacity limited the contribution of mixed systems to aqSOA light absorption. This suggests a weaker radiative effect of BrC from mixed photosensitizer systems than BrC from single photosensitizer systems. Furthermore, more oxygenated and oxidized aqSOA was observed with increasing complexity of the reaction systems (e.g., VL* < VL + ActSyr + SyrAld < VL + ActSyr + SyrAld + GUA). This work offers new insights into aqSOA formation by emphasizing the dual role of organic photosensitizers as oxidant sources and oxidizable substrates.
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  • 文章类型: Journal Article
    自1900年的第一份报告以来,光动力疗法(PDT)一直是人们感兴趣的话题,但尚未成为医学领域的“主流”治疗方案。有明确的迹象表明,PDT可能是“选择的方法”,但是不太可能有治疗全身性疾病的方案。本报告讨论了促进PDT疗效的最新进展,在已知的背景下。还指出了可能限制这些应用范围的因素。这些发展中更有趣的是使用配制技术来靶向特定的细胞器以光损伤。这可以增强对PDT的反应并避免受损的死亡途径干扰PDT功效的情况。
    Photodynamic therapy (PDT) has been a topic of interest since the first report in 1900 but has yet to become a \'mainstream\' treatment protocol in the medical field. There are clear indications for which PDT might be the \'method of choice\', but it is unlikely that there will be protocols for the treatment of systemic disease. This report discusses recent developments for promoting PDT efficacy, in the context of what is already known. Factors that can limit the scope of these applications are also indicated. Among the more interesting of these developments is the use of formulation techniques to target specific organelles for photodamage. This can enhance responses to PDT and circumvent situations where an impaired death pathway interferes with PDT efficacy.
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  • 文章类型: Journal Article
    碳-半导体混合量子点是具有掺杂有选择的纳米级半导体的核心碳纳米颗粒的经典碳点。具体来说,那些掺杂了纳米TiO2的,表示为CTiO2-点,他们的合成和彻底的表征以前报道。在这项工作中,评价了CTiO2-Dot的可见光激活抗菌功能,结果表明,不仅可以有效杀死革兰氏阳性细菌,而且可以有效杀死通常具有更高抗性的革兰氏阴性细菌。混合点显然是比它们的纯碳点对应物更有效的抗菌剂。机械上,CTiO2-Dots的较高抗菌性能归因于其优异的光激发态性能,它们被观察到的更亮的荧光发射所反射。还考虑并讨论了由于纳米级TiO2通过其掺杂的核碳纳米颗粒的光敏化而对抗菌活性做出额外贡献的可能性。
    Carbon-semiconductor hybrid quantum dots are classical carbon dots with core carbon nanoparticles doped with a selected nanoscale semiconductor. Specifically, on those with the nanoscale TiO2 doping, denoted as CTiO2-Dots, their synthesis and thorough characterization were reported previously. In this work, the CTiO2-Dots were evaluated for their visible light-activated antibacterial function, with the results showing the effective killing of not only Gram-positive but also the generally more resistant Gram-negative bacteria. The hybrid dots are clearly more potent antibacterial agents than their neat carbon dot counterparts. Mechanistically, the higher antibacterial performance of the CTiO2-Dots is attributed to their superior photoexcited state properties, which are reflected by the observed much brighter fluorescence emissions. Also considered and discussed is the possibility of additional contributions to the antibacterial activities due to the photosensitization of the nanoscale TiO2 by its doped core carbon nanoparticles.
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  • 文章类型: Journal Article
    蛋白质是生物体和组织中最丰富的生物分子,也存在于许多天然和加工食品和饮料中。以及药物和治疗学。当暴露于紫外可见光时,含有内源性或外源性发色团的蛋白质可以经历直接和间接的光化学过程,导致蛋白质修饰,包括残基的氧化,交联,蛋白水解,共价结合到分子和界面,和构象变化。当这些修改在生理环境中以不受控制的方式发生时,它们会导致生物功能障碍,最终导致细胞死亡。然而,涉及光活化蛋白质修饰的合理设计策略已被证明是调节蛋白质功能甚至构建新生物材料的有价值的工具。这篇小型评论描述了蛋白质中光化学过程的基本原理,并探讨了它们的一些新兴生物医学和纳米生物技术应用,如光动力疗法(PDT),用于伤口愈合的光bonding,光生物打印,用于传感的生物传感器和酶的光固定,和生物催化,在其他人中。
    Proteins are the most abundant biomolecules in living organisms and tissues and are also present in many natural and processed foods and beverages, as well as in pharmaceuticals and therapeutics. When exposed to UV-visible light, proteins containing endogenous or exogenous chromophores can undergo direct and indirect photochemical processes, resulting in protein modifications including oxidation of residues, cross-linking, proteolysis, covalent binding to molecules and interfaces, and conformational changes. When these modifications occur in an uncontrolled manner in a physiological context, they can lead to biological dysfunctions that ultimately result in cell death. However, rational design strategies involving light-activated protein modification have proven to be a valuable tool for the modulation of protein function or even for the construction of new biomaterials. This mini-review describes the fundamentals of photochemical processes in proteins and explores some of their emerging biomedical and nanobiotechnological applications, such as photodynamic therapy (PDT), photobonding for wound healing, photobioprinting, photoimmobilization of biosensors and enzymes for sensing, and biocatalysis, among others.
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  • 文章类型: Journal Article
    缺血性中风成为死亡和残疾的主要原因。它可以由于血管内或心脏血栓栓塞而发展。反映不同中风机制的动物模型仍在开发中。使用光化学血栓形成,我们根据血栓位置开发了一个可行的斑马鱼模型(脑内与心内)。我们使用实时成像和溶栓剂验证了该模型。
    我们使用转基因斑马鱼幼虫(flk:gfp),在内皮细胞中表达特异性荧光。我们注射了玫瑰红,光敏剂作为光敏剂的混合物,和荧光剂进入幼虫的主静脉。然后,我们通过暴露于共焦激光(560nm)并染色血流(RITC-葡聚糖)诱导血栓形成来评估体内实时血栓形成。我们通过检查组织纤溶酶原激活物(tPA)的活性来验证脑内和心内血栓形成模型。
    光化学药物诱导转基因斑马鱼脑内血栓形成。实时成像技术证实了血栓的形成。在体内模型中观察到血管内皮细胞的损伤和凋亡。通过使用光血栓形成的相同方法建立了心内血栓形成模型,并通过tPA溶栓对模型进行验证。
    我们开发并验证了两种容易获得的斑马鱼血栓模型,成本效益高,和直观的评估溶栓药物的疗效。这些模型可用于广泛的未来研究,如筛选和新的抗血栓药物的疗效评估。
    UNASSIGNED: Ischemic stroke becomes a major cause of death and disability. It can develop due to intravascular or cardiac thromboemboli. Animal models that reflect diverse stroke mechanisms remain under development. Using photochemical thrombosis, we developed a feasible zebrafish model according to the thrombus location (intracerebral vs. intracardiac). We validated the model using real-time imaging and thrombolytic agent.
    UNASSIGNED: We used transgenic zebrafish larvae (flk:gfp), which express specific fluorescence in endothelial cells. We injected Rose Bengal, a photosensitizer as a mixture of photosensitizer, and a fluorescent agent into the cardinal vein of the larvae. We then evaluated real-time thrombosis in vivo by inducing thrombosis through exposure to a confocal laser (560 nm) and staining the blood flow (RITC-dextran). We validated intracerebral and intracardiac thrombotic models with checking the activity of tissue plasminogen activator (tPA).
    UNASSIGNED: The photochemical agent induced the formation of intracerebral thrombi in transgenic zebrafish. Real-time imaging techniques confirmed the formation of the thrombi. The damage and apoptosis of the vessel\'s endothelial cells were seen in the in vivo model. An intracardiac thrombosis model was developed by the same method using photothrombosis, and the model was validated through thrombolysis by tPA.
    UNASSIGNED: We developed and validated two zebrafish thrombosis models that are readily available, cost-effective, and intuitive for assessing the efficacy of thrombolytic agents. These models can be used for a broad spectrum of future studies, such as screening and efficacy assessment of new antithrombotic agents.
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  • 文章类型: Journal Article
    在大约2周的时间里,5头成年肉牛在被转移到有芸苔属植物覆盖的田地后不久,在面部和颈部出现了严重的坏死性皮肤损伤。萝卜.我们在这里描述临床症状,血液学,和血清化学结果,以及大体和组织病理学发现,从这次爆发。我们根据与先前报道的世界其他地区BALD病例的历史和诊断结果的相似性,对芸苔属相关肝病(BALD)进行了推定诊断。以前在北美的牛中没有BALD的报道,根据我们的知识,尽管越来越多地使用覆盖作物来改善土壤条件并为牲畜提供饲料。在对BALD进行推定诊断后,牛被从萝卜田中移走,生产者没有注意到其他病例。BALD在世界其他地方是众所周知的,兽医和诊断医生应该意识到这种情况,因为覆盖作物的使用量可能会继续增加。
    Over a period of ~2 wk, 5 adult beef cows developed severe necrotizing skin lesions on the face and neck shortly after being moved to a field with a cover crop of Brassica spp. turnips. We describe here the clinical signs, hematology, and serum chemistry results, as well as gross and histopathologic findings, from this outbreak. We made a presumptive diagnosis of Brassica-associated liver disease (BALD) based on the similarities in the history and diagnostic findings observed with previously reported cases of BALD from elsewhere in the world. BALD has not been reported previously in cattle in North America, to our knowledge, despite the increasing usage of cover crops to improve soil conditions and provide forage for livestock. After the presumptive diagnosis of BALD was made, the cattle were removed from the turnip field and no additional cases were noted by the producer. BALD is well known in other parts of the world, and veterinarians and diagnosticians should be aware of this condition given that the usage of cover crops is likely to continue to increase.
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  • 文章类型: Journal Article
    常用的过氧二硫酸盐(PS)或过氧单硫酸盐(PMS)活化方法由于存在一定的缺陷而在实际应用中受到限制,例如高成本,高能耗和二次污染。在这项研究中,基于染料的光敏性能,构建了无催化剂的茜素绿(AG)自活化PMS催化体系,最终实现了染料活化剂的有效降解,也是目标污染物。这里,52.5%的10mg/LAG的100mL混合物在可见光照射下用1mMPMS在60分钟内分解,从而显示出强的pH适应性。揭示了AG自激活PMS的机理,光激发的AG可以有效地将光生电子转移到PMS中进行激活。产生以单线态氧(1O2)为主的反应性氧化物质,并补充羟基(·OH),超氧自由基(O2•-)和硫酸根自由基(SO4•-)实现了染料污染物的高效自降解。此外,这种自催化系统在自然阳光照射下运行良好,在实际废水处理中具有很大的应用潜力。在这里,光敏染料作为一种理想的PMS活化剂,实现了其高效的自降解,这为以高效低耗的方式开发废水处理工艺提供了一种“利用废物处理废物”的新思路。
    Commonly used peroxydisulfate (PS) or peroxymonosulfate (PMS) activation methods have been limited in their practical application due to certain drawbacks, such as high cost, high energy consumption and secondary pollution. In this study, a catalyst-free alizarin green (AG) self-activating PMS catalytic system was constructed based on photosensitization properties of dye, which ultimately achieved efficient degradation of the dye activator, also the target pollutant. Here, 52.5% of the 100 mL mixture of 10 mg/L AG decomposed within 60 min with 1 mM PMS under visible-light irradiation, thereby showing a strong pH adaptation. Mechanism of AG self-activating PMS was revealed that the photo-excited AG can effectively transfer photo-induced electrons to PMS for its activation, which generates reactive oxidizing species dominated by singlet oxygen (1O2), and supplemented by hydroxyl radical (•OH), superoxide radical (O2•-) and sulfate radical (SO4•-) to realize the efficient self-degradation of the dye pollutants. Moreover, such self-catalytic system operated well under natural sunlight irradiation, indicating the great application potential in the actual wastewater treatment. Herein, photosensitive dye acted as an ideal PMS activator realizing its efficient self-degradation, which provides a novel idea of \"using waste to treat waste\" for developing wastewater treatment process in a high-efficiency and low-consumption way.
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    文章类型: Preprint
    一个基本的,介绍了通用光敏剂的光活化以及随后的能量转移到内源性氧的量子力学描述,这是光动力疗法(PDT)过程中II型光损伤途径的一部分。PS和分子氧近似为双电子分子。在整个四阶段过程中,通过选择规则遵守两分子系统的能量守恒和角动量守恒。包括初始状态,光子被PS吸收,通过系统间交叉(ISC)将PS转化为激发的自旋三重态,以及分子氧通过电子与PS的三重态-三重态交换跃迁到激发的自旋单重态。提供的光敏化描述将为学生和研究人员提供PDT的基本介绍,同时为更广泛的量子力学和物理化学学生提供了应用中量子系统的高级示例,医学背景。
    A fundamental, Quantum Mechanical description of photoactivation of a generic photosensitizer and the ensuing transfer of energy to endogenous oxygen as part of the Type II pathway to photodamage during photodynamic therapy (PDT) is presented. The PS and molecular oxygen are approximated as two-electron molecules. Conservation of energy and of angular momenta of the two molecule system are abided via selection rules throughout the four-stage process, including initial states, absorption of a photon by the PS, conversion of the PS to an excited spin triplet via intersystem crossing (ISC), and the transition of molecular oxygen to an excited spin singlet state via a Triplet-Triplet Exchange of electrons with the PS. The provided description of photosensitization will provide students and researchers with a fundamental introduction to PDT, while offering the broader population of Quantum Mechanics and Physical Chemistry students an advanced example of quantum systems in an applied, medical context.
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  • 文章类型: Journal Article
    光动力抗菌化学疗法(PACT)被广泛研究作为一种战略方法,以灭活废水中的病原微生物,以解决与氯化相关的局限性。臭氧化,和紫外线照射作为消毒方法,这通常会促进抗性基因和有害副产物如三卤甲烷的发展。PACT依赖于光子,氧气,和光敏剂,通过产生活性氧来诱导对各种微生物的细胞毒性作用。光敏剂如卟啉已经通过PACT证明了显著的微生物灭活作用,因此,现在探索废水光处理。这篇综述旨在评估卟啉和卟啉共轭物作为光敏剂用于废水光灭活的功效。还评估了与光敏剂在水处理中的应用有关的担忧。这包括当固定在固体支持物上时光敏剂的回收和再利用。
    Photodynamic antimicrobial chemotherapy (PACT) is extensively studied as a strategic method to inactivate pathogenic microbes in wastewater for addressing the limitations associated with chlorination, ozonation, and ultraviolet irradiation as disinfection methods, which generally promote the development of resistant genes and harmful by-products such as trihalomethanes. PACT is dependent on photons, oxygen, and a photosensitizer to induce cytotoxic effects on various microbes by generating reactive oxygen species. Photosensitizers such as porphyrins have demonstrated significant microbial inactivation through PACT, hence now explored for wastewater phototreatment. This review aims to evaluate the efficacy of porphyrins and porphyrin-conjugates as photosensitizers for wastewater photoinactivation. Concerns relating to the application of photosensitizers in water treatment are also evaluated. This includes recovery and reuse of the photosensitizer when immobilized on solid supports.
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