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Peptide-bridged bis-porphyrin compounds: A photophysical and molecular dynamics study 肽桥联双卟啉化合物:光物理和分子动力学研究
IF 3.261 Pub Date : 2023-08-01 Epub Date: 2023-06-13 DOI: 10.1016/j.jpap.2023.100191
Rita Cimino , Emanuela Gatto , Marta De Zotti , Fernando Formaggio , Claudio Toniolo , Micaela Giannetti , Antonio Palleschi , Carlos Serpa , Mariano Venanzi

Covalently linked peptide-porphyrin compounds are most suitable systems for fundamental studies aiming to the comprehension of the mechanisms driving photoinduced energy/electron transfer processes. Mimicking photosynthetic units, the porphyrin groups act as antenna moieties while the peptide chain is the active medium through which energy and/or electron funneling occur. In this contribution we studied the transfer of excitation between two identical tetraphenylporphyrin groups connected by short peptide chains of different length formed by non-coded conformationally constrained α-amino acids, i.e., Cα-methylvaline. The photophysical events following porphyrin photoexcitation were characterized from the microsecond to the picosecond time region by time-resolved spectroscopy techniques. Ultrafast transient absorption measurements revealed the presence of a transient species that we assign to a self-trapped exciton migrating through the peptide chain. The exciton species propagates the electronic coupling between the two porphyrin groups giving rise to a characteristic bisignate band measured by circular dichroism experiments. Molecular dynamics simulations strongly suggest that the long lifetime (hundreds of picoseconds) of the exciton species is determined by the rigidity of the Cα-methylvaline residues, that inhibited energy relaxation pathways coupled to torsional motions of the peptide chain.

共价连接的肽-卟啉化合物是最适合用于基础研究的体系,旨在理解驱动光诱导能量/电子转移过程的机制。与光合单位类似,卟啉基团充当天线部分,而肽链是能量和/或电子聚集发生的活性介质。在这篇论文中,我们研究了两个相同的四苯基卟啉基团之间的激发转移,这些基团由非编码构象约束α-氨基酸(即c - α-甲基缬氨酸)形成的不同长度的短肽链连接。利用时间分辨光谱技术对卟啉光激发后的光物理事件进行了从微秒到皮秒的时间域表征。超快瞬态吸收测量揭示了瞬态物种的存在,我们将其分配给通过肽链迁移的自捕获激子。激子种在两个卟啉基团之间传播电子耦合,从而产生通过圆二色性实验测量的特征双色带。分子动力学模拟强烈表明,激子的长寿命(数百皮秒)是由c α-甲基缬氨酸残基的刚性决定的,它抑制了与肽链扭转运动耦合的能量松弛途径。
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引用次数: 0
Recent advances in visible light mediated photoinduced aryl radical generation and its application in synthesis 可见光介导光诱导芳基自由基生成及其在合成中的应用研究进展
IF 3.261 Pub Date : 2023-08-01 Epub Date: 2023-06-14 DOI: 10.1016/j.jpap.2023.100192
Tubai Ghosh , Sougata Santra , Grigory V. Zyryanov , Brindaban C. Ranu

The reactions involving aryl radicals is an efficient strategy for the synthesis of a wide variety of important molecules. We have highlighted here recent developments on the generation of aryl radicals from various substrates by visible light mediated photocatalysis and their reactions with different substrates to produce a library of arylated and het-arylated compounds. These reactions are performed at room temperature using LED bulbs. Thus, this strategy is green involving less energy.

涉及芳基自由基的反应是合成多种重要分子的有效策略。我们在此重点介绍了通过可见光介导的光催化从各种底物生成芳基自由基的最新进展,以及它们与不同底物的反应,以产生芳基化和半芳基化化合物库。这些反应是在室温下使用LED灯泡进行的。因此,这种策略是绿色的,涉及较少的能源。
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引用次数: 0
Concise review on seaweed photosynthesis: From physiological bases to biotechnological applications 海藻光合作用研究综述:从生理基础到生物技术应用
IF 3.261 Pub Date : 2023-08-01 Epub Date: 2023-06-15 DOI: 10.1016/j.jpap.2023.100194
Aline P. Martins , Pio Colepicolo , Nair S. Yokoya

Seaweeds play an important role for the environment, since they are photosynthetic organisms, contributing to the cycling of nutrients and to the protection and feeding of several animals. The potential for biotechnological applications of marine macroalgae biomass is enormous, and to attend the demand of the current market, the knowledge of the physiological characteristics of these organisms is essential to ensure a high productivity in cultivation systems. In this review, we contribute to the knowledge about the photosynthetic characteristics of seaweeds, describing relevant aspects of marine macroalgae and photosynthesis, and the biotechnological use of these organisms.

海藻对环境起着重要作用,因为它们是光合生物,有助于营养物质的循环,并保护和喂养几种动物。海洋巨藻生物质生物技术应用的潜力是巨大的,为了满足当前市场的需求,了解这些生物的生理特性对于确保培养系统的高生产力至关重要。本文综述了海藻的光合特性,介绍了海洋大型藻类与光合作用的相关方面,以及这些生物的生物技术应用。
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引用次数: 0
The inhibitory and inactivating effects of visible light on SARS-CoV-2: A narrative update 可见光对SARS-CoV-2的抑制和灭活作用:叙述更新
IF 3.261 Pub Date : 2023-06-01 Epub Date: 2023-05-24 DOI: 10.1016/j.jpap.2023.100187
Shelley Gorman

Prior to the coronavirus disease-19 (COVID-19) pandemic, the germicidal effects of visible light (λ = 400 – 700 nm) were well known. This review provides an overview of new findings that suggest there are direct inactivating effects of visible light – particularly blue wavelengths (λ = 400 – 500 nm) – on exposed severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) virions, and inhibitory effects on viral replication in infected cells. These findings complement emerging evidence that there may be clinical benefits of orally administered blue light for limiting the severity of COVID-19. Possible mechanisms of action of blue light (e.g., regulation of reactive oxygen species) and important mediators (e.g., melatonin) are discussed.

在2019冠状病毒病(COVID-19)大流行之前,可见光(λ = 400 - 700 nm)的杀菌作用众所周知。本文综述了一些新发现,这些发现表明可见光——特别是蓝色波长(λ = 400 - 500 nm)——对暴露的严重急性呼吸综合征冠状病毒2 (SARS-CoV-2)病毒粒子有直接灭活作用,并对感染细胞中的病毒复制有抑制作用。这些发现补充了新出现的证据,即口服蓝光可能对限制COVID-19的严重程度有临床益处。讨论了蓝光可能的作用机制(如对活性氧的调节)和重要的介质(如褪黑激素)。
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引用次数: 0
Photoreceptor contributions to the human pupil light reflex 光感受器对人类瞳孔光反射的贡献
IF 3.261 Pub Date : 2023-06-01 Epub Date: 2023-04-02 DOI: 10.1016/j.jpap.2023.100178
Pablo A. Barrionuevo , Luis A. Issolio , Constanza Tripolone

The pupil reacts to the amount of light reaching the eye. It reduces its size when the light is high and dilates at low light levels to allow the entrance of more photons. This behavior is called pupil light reflex (PLR). Recent investigations in humans were conducted to understand how the photoreceptor signals are combined to drive the pupil light reflex. This review is about the physiological processes that govern the pupil in humans. In particular, how cone-opsins, rhodopsin, and melanopsin photoreception contribute to governing the PLR. We also summarize investigations on the assessment of the PLR in clinical settings.

瞳孔对到达眼睛的光线量作出反应。当光线较强时,它会缩小尺寸,在光线较弱时,它会膨胀,以允许更多的光子进入。这种行为被称为瞳孔光反射(PLR)。最近在人类身上进行的研究是为了了解光感受器信号是如何结合起来驱动瞳孔光反射的。这篇综述是关于控制人类瞳孔的生理过程。特别是锥视蛋白、视紫红质和黑视蛋白的光接受作用如何影响PLR。我们还总结了临床环境中评估PLR的研究。
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引用次数: 2
Enhanced Fluorescence behavior of Safranine-O by complexing with inorganic clay nanosheets 与无机粘土纳米片络合增强红花碱o的荧光行为
IF 3.261 Pub Date : 2023-06-01 Epub Date: 2023-05-18 DOI: 10.1016/j.jpap.2023.100182
Masbooth Rasa Melechalil , Kyosuke Arakawa , Yugo Hirade , Fazalurahman Kuttassery , Tetsuya Shimada , Tamao Ishida , Shinsuke Takagi

Our laboratory has been studying the strong enhancement in the fluorescence quantum yield and an excited lifetime of the organic dye molecules on the clay nanosheets and refer to as “Surface-Fixation Induced Emission”. In this study, Safranine-O which is a mono-cationic phenazine-based dye molecule, was used as the organic dye. It has fluorescence enhancement properties on the clay surface due to the suppression of the non-radiative deactivation rate constant (knr) on the clay nanosheets. While Safranine-O in water in the absence of clay nanosheets exhibited the values as 0.068 and 1.09 × 10−9 s for ϕf and τ, those on the clay surface are 0.121 and 1.96 × 10−9 s. knr values in water and on the clay were calculated to be 8.6 × 108 s − 1 and 4.5 × 108 s − 1, respectively. These results can be explained well by the structure fixing and structure resembling effect. This study helps to explore the possibility of utilizing mono-cationic dye molecules for the realization of desired photo-functional materials and photochemical reactions.

我们实验室一直在研究有机染料分子在粘土纳米片上的荧光量子产率和激发寿命的增强,并将其称为“表面固定诱导发射”。本研究以单阳离子苯那嗪基染料分子Safranine-O为有机染料。由于抑制了粘土纳米片上的非辐射失活速率常数(knr),它在粘土表面具有荧光增强特性。在不含粘土纳米片的情况下,水中的safranin - o的ϕ和τ值分别为0.068和1.09 × 10−9 s,而在粘土表面上的ε和τ值分别为0.121和1.96 × 10−9 s。这些结果可以用结构固定效应和结构相似效应来解释。本研究有助于探索利用单阳离子染料分子实现理想的光功能材料和光化学反应的可能性。
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引用次数: 0
Opsins as main regulators of skin biology 视蛋白是皮肤生物学的主要调节因子
IF 3.261 Pub Date : 2023-06-01 Epub Date: 2023-05-24 DOI: 10.1016/j.jpap.2023.100186
Ana Maria de Lauro Castrucci , Maurício S. Baptista , Leonardo Vinicius Monteiro de Assis

Opsins are light-sensitive proteins that are found across the animal kingdom. In mammals, opsins are classically associated with image-forming processes, a function exerted by cone and rod opsins. In early 2000, melanopsin was identified in the human retina as an important regulator of non-image forming events such as melatonin suppression, pupillary constriction, and circadian rhythm adjustment. The presence of different opsins and the biological processes that these proteins regulate in the skin are increasingly being described. Currently, opsins are considered light as well as thermosensors in the skin. However, additional regulatory functions, in a light and thermo-independent fashion, mostly likely via protein-protein interaction have set a new field of study. The goal of this review is to critically revise the literature on the role of opsins in skin physiology as well as in melanoma cancer.

视蛋白是一种光敏蛋白,在动物界随处可见。在哺乳动物中,视蛋白通常与视锥蛋白和视杆蛋白发挥的图像形成过程有关。2000年初,黑视素在人类视网膜中被确定为褪黑激素抑制、瞳孔收缩和昼夜节律调节等非图像形成事件的重要调节因子。不同视蛋白的存在和这些蛋白在皮肤中调节的生物过程越来越多地被描述。目前,视蛋白被认为是皮肤中的轻热传感器。然而,在光和热无关的方式下,主要可能通过蛋白质-蛋白质相互作用的其他调节功能已经建立了一个新的研究领域。这篇综述的目的是批判性地修订有关视蛋白在皮肤生理和黑色素瘤癌中的作用的文献。
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引用次数: 0
The role of the epidermal physode layer in UV protection of Fucus species 墨角藻表皮植酸层在紫外线防护中的作用
IF 3.261 Pub Date : 2023-06-01 Epub Date: 2023-03-17 DOI: 10.1016/j.jpap.2023.100174
Rafael Meichssner , Mira Wilkens , Frauke Pescheck , Wolfgang Bilger

Phlorotannins are believed to provide UV protection in brown algae. In Fucus species, phlorotannin-rich vesicles (“physodes”) form an “epidermal physode layer”, which might represent the anatomical structure responsible for UV protection. However, this layer has been neglected so far; instead, phlorotannin contents of entire thalli were studied in UV exposure experiments.

We employed fluorometric methods to investigate in which wavelength region and to which degree the epidermal physode layer of two Fucus species reduces the transmittance of UV radiation. For comparison, we also studied Saccharina latissima, a brown algal species without epidermal physode layer.

We could show that the epidermal physode layer absorbs throughout the entire UV wavelength range and reduces the epidermal UV-B transmittance into the thallus strongly (15% transmitted in F. vesiculosus vs. 80–100% in S. latissima). UV-B transmittances varied with growth depth and the variations correlated with photosystem II (PSII) stress responses upon artificial UV-B illumination. We found that the UV-B protection is more than sufficient for natural UV-B levels and of rather constitutive nature.

In conclusion, the epidermal physode layer appears to be the anatomical feature exerting UV protection by phlorotannins in Fucus species and might thus be a core adaptation that enables Fucales the colonization of the intertidal habitat.

褐藻中的绿单宁被认为可以保护紫外线。在Fucus物种中,富含植酸的囊泡(“physode”)形成“表皮植酸层”,这可能代表了负责紫外线防护的解剖结构。然而,到目前为止,这一层一直被忽视;采用紫外照射实验研究了整个菌体的植绿素含量。采用荧光光度法研究了两种真菌表皮藻质层在哪个波长区域以及在多大程度上降低了紫外线的透过率。为了进行比较,我们还研究了一种没有表皮藻皮层的褐藻Saccharina latissima。我们可以发现,表皮植酸层在整个紫外波长范围内吸收紫外线,并强烈降低表皮紫外线b进入菌体的透过率(在水疱F. vesiculosus中透过率为15%,而在横条S. latissima中透过率为80-100%)。UV-B透过率随生长深度的变化而变化,其变化与光系统II (PSII)在人工UV-B照射下的胁迫响应相关。我们发现紫外线- b的保护是绰绰有余的自然紫外线- b水平和相当本构性。综上所述,表皮植酸层似乎是Fucales物种中发挥紫外线保护作用的解剖特征,因此可能是Fucales在潮间带栖息地定居的核心适应。
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引用次数: 0
Endocytic internalization mechanism of bioactive antibacterial nanoparticles by fibroblasts 生物活性抗菌纳米颗粒在成纤维细胞中的内吞内化机制
IF 3.261 Pub Date : 2023-06-01 Epub Date: 2023-04-13 DOI: 10.1016/j.jpap.2023.100179
Maryam Ghaffari , Anil Kishen , Annie Shrestha

Studying the uptake mechanism of photosensitizers is an important step in developing an ideal photosensitizer for use in photodynamic therapy (PDT). Understanding the uptake mechanism can help design novel photosensitizers that are selectively accumulated in the target tissue, with improved pharmacokinetics, and are dosed optimally to maximize the efficacy of the treatment. In our previous studies we synthesized and characterized the use of chitosan nanoparticles functionalized with rose bengal (CSRBnp) as a photosensitizer against dental biofilm. The aim of this study is to analyze the internalization mechanism and cellular proinflammatory activities of CSRBnps on fibroblasts. Fibroblasts (NIH 3T3) were incubated with chlorpromazine (5 µg/ml), nystatin (5 µg/ml), wortmannin (100 ng/ml) and at 4 °C for 30 min followed by CSRBnp (0.3 mg/ml). Cell viability (MTS assay), intracellular adenosine triphosphate content (Luminescence assay), cytokine expression (TNF-α) using ELISA and nitric oxide (NO) production by Griess reaction system were conducted at different time intervals (30 min, 1, 4, and 12 h). The internalization of CSRBnps was analyzed using live cell imaging confocal microscope with excitation wavelengths of 405 and 568 to detect nuclei (Hoechst 33,342) and CSRBnps respectively. CSRBnps and inhibitors at the applied concentrations were not cytotoxic. ATP content in chlorpromazine and without inhibitors groups were significantly lower than the control group at 12 h. All inhibitors showed significantly lower CSRBnps uptake compared to the control group at 30 min, 1 h, and 4 h time. Wortmannin resulted in the most significant inhibition of CSRBnps uptake as compared to chlorpromazine and nystatin (P < 0.05). TNF-α expression and NO production were not significant during the entire CSRBnps uptake. The results showed macropinocytosis was a dominant CSRBnps uptake mechanism by fibroblasts in the early stages and non-specific uptake pathways were activated after prolonged incubation time. CSRBnps uptake by fibroblasts was energy dependent and did not cause any proinflammatory response.

研究光敏剂的吸收机制是开发理想的光敏剂用于光动力治疗(PDT)的重要一步。了解吸收机制可以帮助设计新的光敏剂,选择性地在靶组织中积累,改善药代动力学,并选择最佳剂量,以最大限度地提高治疗效果。在我们之前的研究中,我们合成并表征了以玫瑰红为功能化的壳聚糖纳米颗粒(CSRBnp)作为牙齿生物膜的光敏剂。本研究的目的是分析CSRBnps在成纤维细胞中的内化机制和细胞促炎活性。成纤维细胞(NIH 3T3)分别与氯丙嗪(5µg/ml)、制霉菌素(5µg/ml)、wortmannin (100 ng/ml)、CSRBnp (0.3 mg/ml)在4℃下孵育30 min。在不同的时间间隔(30 min、1、4、12 h)检测细胞活力(MTS法)、细胞内三磷酸腺苷含量(发光法)、ELISA法检测细胞因子表达(TNF-α)和Griess反应系统产生一氧化氮(NO),利用激发波长为405和568的活细胞成像共聚焦显微镜检测细胞核(Hoechst 33,342)和CSRBnps的内化情况。应用浓度的CSRBnps和抑制剂无细胞毒性。氯丙嗪组和无抑制剂组在12 h时ATP含量显著低于对照组。所有抑制剂在30 min、1 h和4 h时的CSRBnps摄取均显著低于对照组。与氯丙嗪和制霉菌素相比,Wortmannin对CSRBnps摄取的抑制作用最为显著(P <0.05)。在整个CSRBnps摄取过程中,TNF-α的表达和NO的产生均不显著。结果表明,巨量胞饮是成纤维细胞早期摄取CSRBnps的主要机制,非特异性摄取途径在培养时间延长后被激活。成纤维细胞对CSRBnps的摄取是能量依赖性的,不会引起任何促炎反应。
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引用次数: 0
Photophysical and electrochemical properties of 9-naphthyl-3,6-diaminocarbazole derivatives and their application as photosensitizers 9-萘-3,6-二氨基咔唑衍生物的光物理和电化学性质及其作为光敏剂的应用
IF 3.261 Pub Date : 2023-06-01 Epub Date: 2023-03-22 DOI: 10.1016/j.jpap.2023.100176
Ryosuke Matsubara , Huilong Kuang , Tatsushi Yabuta , Weibin Xie , Masahiko Hayashi , Eri Sakuda

A series of 3,6-diamino-9-naphthylcarbazole derivatives were synthesized and characterized experimentally and computationally. As the lowest unoccupied molecular orbital of the naphthyl group has lower energy than that of the phenyl group, a charge transfer from carbazole to naphthyl in the excited states occurred causing solvatofluorochromism and solvent-dependency in fluorescence quantum yields. A molecule having two carbazole substituents sandwiching the central naphthyl ring had absorption reaching 470 nm and a high reducing capability in the excited state. This molecule could successfully photosensitize the hydrodehalogenation of haloarenes under visible light irradiation.

合成了一系列3,6-二氨基-9-萘基咔唑衍生物,并进行了实验和计算表征。由于萘基的最低未占据分子轨道比苯基的能量低,在激发态下,咔唑向萘基发生电荷转移,导致荧光量子产率的溶剂荧光变色和溶剂依赖性。在激发态下,两个咔唑取代基夹在中心环烷环上的分子具有高达470 nm的吸收和高还原能力。该分子能在可见光照射下成功地光敏卤代烃的加氢脱卤反应。
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引用次数: 1
期刊
Journal of Photochemistry and Photobiology
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