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Development of dye-sensitized solar cells using pigment extracts produced by Talaromyces atroroseus GH2 利用 Talaromyces atroroseus GH2 产生的色素提取物开发染料敏化太阳能电池
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-21 DOI: 10.1007/s43630-024-00566-x
Alessia Tropea, Donatella Spadaro, Stefano Trocino, Daniele Giuffrida, Tania Maria Grazia Salerno, Juan Pablo Ruiz-Sanchez, Julio Montañez, Lourdes Morales-Oyervides, Laurent Dufossé, Luigi Mondello, Giuseppe Calogero

The identification of more efficient, clean, secure, and competitive energy supply is necessary to align with the needs of sustainable devices. For this reason, a study for developing innovative dye-sensitized solar cells (DSSCs) based on microbial pigments is reported starting from Talaromyces atroroseus GH2. The fungus was cultivated by fermentation and the extracellular pigment extract was characterized by HPLC-DAD-ESI-MS analyses. The most abundant compound among the 22 azaphilone-type pigments identified was represented by PP-O. The device’s behavior was investigated in relation to electrolyte and pH for verifying the stability on time and the photovoltaic performance. Devices obtained were characterized by UV–vis measurements to verify the absorbance intensity and transmittance percentage. Moreover, photovoltaic parameters through photo-electrochemical measurements (I–V curves) and impedance characteristics by Electrochemical Impedance Spectroscopy (EIS) were determined. The best microbial device showed a short-circuit current density (Jsc) of 0.69 mA/cm2, an open-circuit photo-voltage (Voc) of 0.27 V and a Fill Factor (FF) of 0.60. Furthermore, the power conversion efficiency (PCE) of the device was 0.11%. Thus, the present study demonstrated the potential of microbial origin pigments for developing DSSCs.

Graphical abstract

为了满足可持续设备的需求,有必要确定更高效、清洁、安全和有竞争力的能源供应。为此,本研究报告了一项基于微生物色素开发创新型染料敏化太阳能电池(DSSC)的研究,该研究以 Talaromyces atroroseus GH2 为起点。研究人员通过发酵培养了这种真菌,并通过 HPLC-DAD-ESI-MS 分析对胞外色素提取物进行了表征。在鉴定出的 22 种萘醌型色素中,含量最高的化合物是 PP-O。研究了该装置的行为与电解质和 pH 值的关系,以验证其时间稳定性和光伏性能。通过紫外-可见光测量,验证了所获得器件的吸光强度和透射率。此外,还通过光电化学测量(I-V 曲线)确定了光伏参数,并通过电化学阻抗谱(EIS)确定了阻抗特性。最佳微生物装置的短路电流密度(Jsc)为 0.69 mA/cm2,开路光电电压(Voc)为 0.27 V,填充因子(FF)为 0.60。此外,该器件的功率转换效率(PCE)为 0.11%。因此,本研究证明了微生物源色素在开发 DSSC 方面的潜力。
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引用次数: 0
Light-emitting plants development by inoculating of Vibrio campbellii RMT1 on the rhizospheric zone of Aglaonema cochinchinense 通过将 Campbelli弧菌 RMT1 接种到 Aglaonema cochinchinense 的根瘤区来培育发光植物
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-16 DOI: 10.1007/s43630-024-00568-9
Chutipa Kanjanapokin, Paitip Thiravetyan, Nattida Chonjoho, Rujira Dolphen, Chairat Treesubsuntorn

The concept of utilizing light-emitting plants (LEPs) as an alternative to traditional electricity-based lighting has garnered interest. However, challenges persist due to the need for genetic modification or chemical infusion in current LEPs. To address this, researchers have investigated the interaction between plants and luminous bacteria, specifically Vibrio campbellii, which can efficiently be translocated into Aglaonema cochinchinense tissues through the roots to produce LEPs. This study concentrated on examining light intensity and enhancing luminescence by growing plants and spraying them with various media substances. The results indicated that V. campbellii successfully translocated into the plant tissue via the root system and accumulated a high number of bacteria in the stems, approximately 8.46 × 104 CFU/g, resulting in a light-emitting intensity increase of 12.13-fold at 48 h, and then decreased after 30 h. Interestingly, luminescence stimulation by spraying the growth medium managed to induce the highest light emission, reaching 14.84-fold at 48 h, though it had some negative effects on the plant. Conversely, spraying plants with CaCl2 on the leaves prolonged light emission for a longer duration (42 h after spraying) and had a positive effect on plant health, it maintained ion homeostasis and reduced-MDA content. This study highlights the potential of using V. campbellii and CaCl2 spraying for the future development of practical light-emitting plants.

Graphical abstract

利用发光植物替代传统电力照明的概念已引起人们的兴趣。然而,由于目前的发光植物需要进行基因改造或注入化学物质,因此挑战依然存在。为了解决这个问题,研究人员研究了植物与发光细菌(特别是坎贝尔弧菌)之间的相互作用,坎贝尔弧菌可以通过根部有效地转移到 Aglaonema cochinchinense 组织中,从而产生 LEPs。这项研究的重点是通过种植植物和向其喷洒各种培养基物质来检测光照强度和增强发光能力。结果表明,V.campbellii 通过根系成功转移到植物组织中,并在茎中积累了大量细菌,约为 8.46 × 104 CFU/g,导致发光强度在 48 小时内增加了 12.13 倍,30 小时后又有所下降。有趣的是,通过喷洒生长培养基来刺激发光,能够诱导最高的光发射,在 48 小时内达到 14.84 倍,但对植物有一些负面影响。相反,向植物叶片喷洒 CaCl2 能延长发光时间(喷洒后 42 小时),并对植物健康产生积极影响,它能维持离子平衡并降低 MDA 含量。这项研究强调了利用坎贝尔藻和 CaCl2 喷雾在未来开发实用发光植物方面的潜力。 图文摘要
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引用次数: 0
The contradictory role of febuxostat in ABCG2 expression and potentiating hypericin-mediated photodynamic therapy in colorectal cancers 非布索坦在结直肠癌 ABCG2 表达和增效金丝桃素介导的光动力疗法中的矛盾作用
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-16 DOI: 10.1007/s43630-024-00575-w
Aaron King, Thomas Maisey, Erica L. Harris, James A. Poulter, David G. Jayne, M. Ibrahim Khot

Photodynamic Therapy (PDT) is an emerging method to treat colorectal cancers (CRC). Hypericin (HYP) is an effective mediator of PDT and the ABCG2 inhibitor, Febuxostat (FBX) could augment PDT. HT29 and HEK293 cells showed light dependant cytotoxic response to PDT in both 2D and 3D cell models. FBX co-treatment was not found to improve PDT cytotoxicity. Next, ABCG2 protein expression was observed in HT29 but not in HEK293 cells. However, ABCG2 gene expression analysis did not support protein expression results as ABCG2 gene expression results were found to be higher in HEK293 cells. Although HYP treatment was found to significantly reduce ABCG2 gene expression levels in both cell lines, FBX treatment partially restored ABCG2 gene expression. Our findings indicate that FBX co-treatment may not be suitable for augmenting HYP-mediated PDT in CRC but could potentially be useful for other applications.

Graphical Abstract

光动力疗法(PDT)是治疗结直肠癌(CRC)的一种新兴方法。金丝桃素(HYP)是光动力疗法的有效介质,而ABCG2抑制剂非布索坦(FBX)可以增强光动力疗法。在二维和三维细胞模型中,HT29和HEK293细胞对PDT表现出光依赖性细胞毒性反应。发现 FBX 联合治疗并不能提高 PDT 的细胞毒性。接着,在 HT29 细胞中观察到 ABCG2 蛋白表达,但在 HEK293 细胞中没有观察到。然而,ABCG2 基因表达分析并不支持蛋白表达结果,因为在 HEK293 细胞中 ABCG2 基因表达结果更高。虽然发现 HYP 处理能显著降低两种细胞系中 ABCG2 基因的表达水平,但 FBX 处理能部分恢复 ABCG2 基因的表达。我们的研究结果表明,FBX 联合治疗可能不适合增强 HYP 介导的 PDT 在 CRC 中的作用,但有可能在其他应用中发挥作用。
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引用次数: 0
Characterization and evaluation of photolabile (µ-peroxo)(µ-hydroxo)bis[bis(bipyridyl)cobalt caged oxygen compounds to facilitate time-resolved crystallographic studies of cytochrome c oxidase 促进细胞色素 c 氧化酶时间分辨晶体学研究的可光敏(µ-过氧)(µ-羟基)双[双(联吡啶)钴笼氧化合物的特性和评估
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-14 DOI: 10.1007/s43630-024-00558-x
Emil Sandelin, Jonatan Johannesson, Ola Wendt, Gisela Brändén, Richard Neutze, Carl-Johan Wallentin

Photolabile (µ-peroxo)(µ-hydroxo)bis[bis(bipyridyl)-cobalt-based caged oxygen compounds have been synthesized and characterized by optical absorbance spectroscopy, X-ray crystallography. and the quantum yield and redox stability were investigated. Furthermore, conditions were established where redox incompatibilities encountered between caged oxygen compounds and oxygen-dependant cytochrome c oxidase (CcO) could be circumvented. Herein, we demonstrate that millimolar concentrations of molecular oxygen can be released from a caged oxygen compound with spatio-temporal control upon laser excitation, triggering enzymatic turnover in cytochrome c oxidase. Spectroscopic evidence confirms the attainment of a homogeneous reaction initiation at concentrations and conditions relevant for further crystallography studies. This was demonstrated by the oxidizing microcrystals of reduced CcO by liberation of millimolar concentrations of molecular oxygen from a caged oxygen compound. We believe this will expand the scope of available techniques for the detailed investigation of oxygen-dependant enzymes with its native substrate and facilitate further time-resolved X-ray based studies such as wide/small angle X-ray scattering and serial femtosecond crystallography.

Graphical abstract

通过光学吸光光谱学和 X 射线晶体学,合成并表征了可光吸收(µ-过氧)(µ-羟基)双[双(联吡啶)-钴基笼式氧化合物,并对其量子产率和氧化还原稳定性进行了研究。此外,我们还确定了可以避免笼氧化合物与依赖氧的细胞色素 c 氧化酶(CcO)之间氧化还原不相容的条件。在这里,我们证明了毫摩尔浓度的分子氧可以在激光激发下从笼氧化合物中释放出来,并具有时空控制能力,从而引发细胞色素 c 氧化酶中的酶转换。光谱学证据证实,在与进一步晶体学研究相关的浓度和条件下,可以实现均匀的反应启动。通过从笼式氧化合物中释放毫摩尔浓度的分子氧来氧化还原型 CcO 的微晶,证明了这一点。我们相信,这将扩大现有技术的范围,以详细研究依赖氧的酶及其原生底物,并促进基于时间分辨 X 射线的进一步研究,例如宽/小角 X 射线散射和串行飞秒晶体学。
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引用次数: 0
The use of natural extracts with photoprotective activity: a 2015–2023 patent prospection 使用具有光保护活性的天然提取物:2015-2023 年专利展望
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-13 DOI: 10.1007/s43630-024-00559-w
Ana Maria Santos Oliveira, Daniel de Souza Batista, Tailaine Nascimento de Castro, Izabel Almeida Alves, Ricardo Bizogne Souto, Milleno Dantas Mota, Mairim Russo Serafini, Gomathi Rajkumar, Edith Cristina Laignier Cazedey

Synthetic sunscreen offers protection against excessive exposure to ultraviolet (UV) radiation from the sun, and protects the skin from possible damage. However, they have low efficacy against the formation of reactive oxygen species (ROS), which are highly reactive molecules that can be generated in the skin when it is exposed to UV radiation, and are known to play a role in oxidative stress, which can contribute to skin aging and damage. Thus, there is an ongoing search for sunscreens that do not have these negative effects. One promising source for these is natural products. Therefore, the current patent review summarizes topical formulations made from natural compounds that have antioxidant properties and can be used as photoprotective or anti-aging agents, either using a single natural extract or a combination of extracts. The review reports basic patent information (applicant country, type of applicant, and year of filing) and gives details about the invention, including its chemical composition, and the in vitro and in vivo tests performed. These patents describe natural products that can be used to protect the skin and validate their efficacy, and safety, in addition to standardizing their formulations. The compositions described illustrate the consistent innovation in the use of natural products to protect against UV damage and photoaging disorders, a promising field which is receiving growing global recognition.

Graphical abstract

合成防晒霜可防止过度暴露于阳光中的紫外线(UV)辐射,保护皮肤免受可能的损伤。活性氧是一种高活性分子,当皮肤暴露在紫外线辐射下时就会产生活性氧,众所周知,活性氧在氧化应激中起作用,而氧化应激会导致皮肤老化和损伤。因此,人们一直在寻找不会产生这些负面影响的防晒剂。其中一个很有前景的来源就是天然产品。因此,本专利综述总结了由天然化合物制成的外用配方,这些天然化合物具有抗氧化特性,可用作光保护剂或抗衰老剂,既可使用单一天然提取物,也可使用多种提取物的组合。综述报告了基本的专利信息(申请人国家、申请人类型和申请年份),并提供了有关发明的详细信息,包括其化学成分以及所进行的体外和体内试验。这些专利介绍了可用于保护皮肤的天然产品,并验证了这些产品的功效和安全性,此外还规范了这些产品的配方。所描述的成分说明了在使用天然产品防止紫外线损伤和光老化疾病方面的持续创新,这是一个前景广阔的领域,正在得到越来越多的全球认可。
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引用次数: 0
miR-1246-overexpressing exosomes improve UVB-induced photoaging by activating autophagy via suppressing GSK3β miR-1246过表达外泌体通过抑制GSK3β激活自噬,改善紫外线诱导的光老化
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-13 DOI: 10.1007/s43630-024-00567-w
Wei Gao, Limin Yuan, Yue Zhang, Fangzhou Huang, Chen Ai, Tianci Lv, Jiale Chen, Hui Wang, Yixin Ling, Yu-shuai Wang

Stem cell paracrine has shown potential application in skin wound repair and photoaging treatment. Our previous study demonstrated that miR-1246-overexpressing Exosomes (OE-EXs) isolated from adipose-derived stem cells (ADSCs) showed superior photo-protecting effects on UVB-induced photoaging than that of the vector, however, the underlying mechanism was unclear. The simultaneous bioinformatics analysis indicated that miR-1246 showed potential binding sites with GSK3β which acted as a negative regulator for autophagy. This study was aimed to explore whether OE-EXs ameliorate skin photoaging by activating autophagy via targeting GSK3β. The results demonstrated that OE-EXs significantly decreased GSK3β expression, enhanced autophagy flux and autophagy-related proteins like LC3II, while suppressed p62 expression. Meanwhile, OE-EXs markedly reversed the levels of intracellular ROS, MMP-1, procollagen type I and DNA damage in human skin fibroblasts caused by UVB irradiation, but the ameliorating effects were significantly inhibited when 3-Methyladenine (3-MA) was introduced to block the autophagy pathway. Further, OE-EXs could reverse UVB-induced wrinkles, epidermal hyperplasia, and collagen fibers reduction in Kunming mice, nevertheless, the therapeutical effects of OE-EXs were attenuated when it was combinative treated with 3-MA. In conclusion, OE-EXs could cure UVB induced skin photoaging by activating autophagy via targeting GSK3β.

Graphical abstract

干细胞旁分泌物在皮肤伤口修复和光老化治疗中具有潜在的应用价值。我们之前的研究表明,从脂肪源性干细胞(ADSCs)中分离出的miR-1246高表达外泌体(OE-EXs)对紫外线诱导的光老化具有比载体更好的光保护作用,但其潜在机制尚不清楚。同时进行的生物信息学分析表明,miR-1246 显示了与 GSK3β 的潜在结合位点,而 GSK3β 是自噬的负调控因子。本研究旨在探讨OE-EX是否能通过靶向GSK3β激活自噬而改善皮肤光老化。结果表明,OE-EXs能显著降低GSK3β的表达,增强自噬通量和自噬相关蛋白(如LC3II),同时抑制p62的表达。同时,OE-EXs 能明显逆转 UVB 照射引起的人皮肤成纤维细胞内 ROS、MMP-1、I 型胶原和 DNA 损伤水平,但当引入 3-Methyladenine (3-MA) 阻断自噬途径时,其改善效果会受到明显抑制。此外,OE-EXs 还能逆转 UVB 引起的昆明小鼠皱纹、表皮增生和胶原纤维减少,但与 3-MA 合用时,OE-EXs 的治疗效果会减弱。总之,OE-EXs可通过靶向GSK3β激活自噬,从而治疗UVB诱导的皮肤光老化。
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引用次数: 0
Exploring the role of impedance spectroscopy in assessing 405 nm laser-induced inactivation of saccharomyces cerevisiae 探索阻抗光谱法在评估 405 纳米激光诱导的酿酒酵母失活中的作用
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-09 DOI: 10.1007/s43630-024-00564-z
Beng Jiong Ang, Nursakinah Suardi, Eugene Boon Beng Ong, Siti Nur Hazieqah Khasim, Sylvester Jande Gemanam, Iskandar Shahrim Mustafa, Jing Heng Fong

Impedance spectroscopy was employed to assess the electrical properties of yeast following 405 nm laser irradiation, exploring the effects of visible, non-ionizing laser-induced inactivation as a more selective and safer alternative for photoinactivation applications compared to the use of DNA targeting, ionizing UV light. Capacitance and impedance spectra were obtained for yeast suspensions irradiated for 10, 20, 30, and 40 min using 100 and 200 mW laser powers. Noticeable differences in capacitance spectra were observed at lower frequencies (40 Hz to 1 kHz), with a significant increase at 40 min for both laser powers. β-dispersion was evident in the impedance spectra in the frequency range of 10 kHz to 10 MHz. The characteristic frequency of dielectric relaxation steadily shifted to higher frequencies with increasing irradiation time, with a drastic change observed at 40 min for both laser powers. These changes signify a distinct alteration in the physical state of yeast. A yeast spot assay demonstrated a decrease in cell viability with increasing laser irradiation dose. The results indicate a correlation between changes in electrical properties, cell viability, and the efficacy of 405 nm laser-induced inactivation. Impedance spectroscopy is shown to be an efficient, non-destructive, label-free method for monitoring changes in cell viability in photobiological effect studies. The development of impedance spectroscopy-based real-time studies in photoinactivation holds promise for advancing our understanding of light-cell interactions in medical applications.

Graphical abstract

采用阻抗光谱评估了酵母在 405 nm 激光照射后的电特性,探索了可见光、非电离激光诱导失活的效果,与使用 DNA 靶向、电离紫外线相比,可见光、非电离激光诱导失活是一种选择性更强、更安全的光失活应用替代方法。使用 100 和 200 mW 激光功率对酵母悬浮液照射 10、20、30 和 40 分钟后,获得了电容和阻抗光谱。在较低频率(40 Hz 至 1 kHz)下观察到电容光谱的明显差异,在 40 分钟时,两种激光功率的电容光谱都有显著增加。在 10 kHz 至 10 MHz 的频率范围内,阻抗谱明显存在 β 分散。随着辐照时间的延长,介电弛豫的特征频率逐渐向更高的频率移动,在 40 分钟时,两种激光功率下的频率都发生了急剧变化。这些变化表明酵母的物理状态发生了明显改变。酵母光斑检测表明,随着激光照射剂量的增加,细胞存活率下降。结果表明,电特性变化、细胞存活率和 405 nm 激光诱导失活的效果之间存在相关性。阻抗光谱法是一种高效、无损、无标记的方法,可用于监测光生物效应研究中细胞活力的变化。开发基于阻抗光谱的光失活实时研究有望促进我们对医疗应用中光-细胞相互作用的理解。
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引用次数: 0
Urinary thymidine dimer excretion reflects personal ultraviolet radiation exposure levels 尿中胸腺嘧啶二聚体排泄量反映个人紫外线辐射水平
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-08 DOI: 10.1007/s43630-024-00563-0
Catharina Margrethe Lerche, Nynne Johanne Sahl Frederiksen, Ida Schwarz Thorsteinsson, Brian Køster, Lars Nybo, Andreas D. Flouris, Jakob Heydenreich, Peter Alshede Philipsen, Merete Hædersdal, Hans Christian Wulf, Jonatan Riber Granborg

Exposure to ultraviolet radiation (UVR) leads to skin DNA damage, specifically in the form of cyclobutane pyrimidine dimers, with thymidine dimers being the most common. Quantifying these dimers can indicate the extent of DNA damage resulting from UVR exposure. Here, a new liquid chromatography-mass spectrometry (LC–MS) method was used to quantify thymidine dimers in the urine after a temporary increase in real-life UVR exposure. Healthy Danish volunteers (n = 27) experienced increased UVR exposure during a winter vacation. Individual exposure, assessed via personally worn electronic UVR dosimeters, revealed a mean exposure level of 32.9 standard erythema doses (SEDs) during the last week of vacation. Morning urine thymidine dimer concentrations were markedly elevated both 1 and 2 days post-vacation, and individual thymidine dimer levels correlated with UVR exposure during the last week of the vacation. The strongest correlation with erythema-weighted personal UVR exposure (Power model, r2 = 0.64, p < 0.001) was observed when both morning urine samples were combined to measure 48-h thymidine dimer excretion, whereas 24-h excretion based on a single sample provided a weaker correlation (Power model, r2 = 0.55, p < 0.001). Sex, age, and skin phototype had no significant effect on these correlations. For the first time, urinary thymidine dimer excretion was quantified by LC–MS to evaluate the effect of a temporary increase in personal UVR exposure in a real-life setting. The high sensitivity to elevated UVR exposure and correlation between urinary excretion and measured SED suggest that this approach may be used to quantify DNA damage and repair and to evaluate photoprevention strategies.

Graphical abstract

紫外线辐射(UVR)会导致皮肤 DNA 损伤,具体表现为环丁烷嘧啶二聚体,其中胸苷二聚体最为常见。对这些二聚体进行定量分析可以显示紫外线照射造成的DNA损伤程度。本文采用一种新型液相色谱-质谱(LC-MS)方法,对实际紫外线照射临时增加后尿液中的胸苷二聚体进行定量。健康的丹麦志愿者(n = 27)在寒假期间经历了紫外线照射增加的情况。通过个人佩戴的电子紫外线剂量计评估个人暴露情况,结果显示假期最后一周的平均暴露水平为 32.9 标准红斑剂量(SEDs)。度假后 1 天和 2 天,晨尿中的胸苷二聚体浓度明显升高,个人胸苷二聚体水平与度假最后一周的紫外线照射量相关。当合并两个晨尿样本以测量 48 小时胸苷二聚体排泄量时,观察到胸苷二聚体与红斑加权个人紫外线照射量的相关性最强(Power 模型,r2 = 0.64,p < 0.001),而基于单个样本的 24 小时排泄量的相关性较弱(Power 模型,r2 = 0.55,p < 0.001)。性别、年龄和皮肤光型对这些相关性没有明显影响。这是首次通过液相色谱-质谱联用仪(LC-MS)对尿中胸腺嘧啶二聚体的排泄进行量化,以评估在现实生活中个人紫外线照射量暂时增加的影响。对紫外线照射升高的高灵敏度以及尿液排泄量与测得的 SED 之间的相关性表明,这种方法可用于量化 DNA 损伤和修复以及评估光预防策略。
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引用次数: 0
Photocatalytic activity enhancement of two-step and one-pot synthesis of Pd/ZnO nanocomposites: an experimental and DFT study 两步法和一步法合成 Pd/ZnO 纳米复合材料的光催化活性增强:实验和 DFT 研究
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-07 DOI: 10.1007/s43630-024-00562-1
María de Lourdes Ruiz Peralta, J. C. Moreno-Hernandez, C. E. Rocha-Díaz, J. H. Camacho-García, A. Escobedo-Morales, U. Salazar-Kuri

Pd/ZnO nanocomposites were successfully synthesized by means of one and two pot synthesis and applied in the photodegradation of Rh6G. The nanocomposites were characterized by XRD, SEM, TEM, FTIR and micro-Raman spectroscopies. It was found the presence of PdZn2, PdO and agglomerated particles in the support surface for the Palladium-based nanocomposites fabricated by one-pot route; the two-step method allowed the formation of spherical Pd nanoparticles, with homogeneous distribution in the nanocomposite matrix, with an average size of 2.16 nm. The results show higher photocatalytic efficiency for the samples fabricated under the two-step approach compared to the one-pot synthesis. Based on experimental results, density functional theory (DFT) calculations were carried out to understand the enhancement photocatalytic of Pd/ZnO nanocomposites. To achieve it, the ZnO (001) and (101) surfaces were built and decorated by different Pd coverages. The theoretical results indicated two different photocatalytic mechanisms. In ZnO (001) case, the electrons flowed from surface to Pd, generating the superoxide radical anion (⋅O2). Furthermore, the density of states of the ZnO (001) surface was modified by impurity Pd–d states at proximity to the conduction states, which may work as electron acceptors states. On the other hand, we found that the electrons flow from Pd to ZnO (101) surface, inducing the formation of ⋅OH and ⋅O2 for the degradation of Rh6G. The density of states of the ZnO (101) revealed a reduction in its bandgap, due to Pd–d states localized above valence states. Hence, our theoretical results suggest that the Pd–d states may facilitate the mobility of electrons and holes in (001) and (101) surfaces, respectively, reducing the rate of charge recombination.

Graphical abstract

通过单锅和双锅合成法成功合成了 Pd/ZnO 纳米复合材料,并将其应用于 Rh6G 的光降解。通过 XRD、SEM、TEM、傅立叶变换红外光谱和微拉曼光谱对纳米复合材料进行了表征。结果表明,采用一锅法制备的钯基纳米复合材料的支撑表面存在 PdZn2、PdO 和团聚颗粒;采用两步法制备的钯基纳米复合材料形成了球形钯纳米颗粒,并在纳米复合材料基体中均匀分布,平均粒径为 2.16 nm。结果表明,与一锅合成法相比,两步法制备的样品具有更高的光催化效率。在实验结果的基础上,进行了密度泛函理论(DFT)计算,以了解 Pd/ZnO 纳米复合材料的光催化增强作用。为了实现这一目标,在 ZnO (001) 和 (101) 表面上建立并装饰了不同的钯覆盖层。理论结果表明了两种不同的光催化机制。在氧化锌(001)的情况下,电子从表面流向钯,产生超氧自由基阴离子(⋅O2-)。此外,ZnO (001) 表面的态密度被靠近传导态的杂质 Pd-d 态所改变,这些态可能是电子受体态。另一方面,我们发现电子从 Pd 流向 ZnO(101)表面,诱导形成⋅OH 和⋅O2-,从而降解 Rh6G。ZnO (101) 的状态密度显示其带隙减小,这是由于 Pd-d 状态定位在价态之上。因此,我们的理论结果表明,Pd-d态可能会分别促进电子和空穴在(001)和(101)表面的迁移,从而降低电荷重组率。
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引用次数: 0
Europium-based β-hydroxyketone complexes: synthesis, optoelectronic, thermal and computational analyses 铕基 β-羟基酮配合物:合成、光电、热和计算分析
IF 3.1 3区 化学 Q1 Chemistry Pub Date : 2024-04-06 DOI: 10.1007/s43630-024-00561-2
Pratibha Ahlawat, Poonam Kumari, Vaishnavi Lather, Bhawna Rathee, Rajesh Kumar

Six red-light-emitting Eu(III) complexes having a β-hydroxyketone as ligand and heterocyclic ring containing compounds as ancillary ligands were synthesized to explore their use in displays and optoelectronics. The coordinating behavior of complexes was determined by various techniques such as FTIR (Fourier transform infrared), 1H-NMR (Nuclear magnetic resonance), and 13C-NMR that establishes a bonding of ligand and ancillary ligand with the Eu(III) ion. Morphology and purity were investigated through XRD (X-ray diffraction), SEM (scanning electron microscopy) and EDS (energy-dispersive X-ray spectroscopy) analyses that suggest semicrystalline and pure complex formation. Thermal analysis of complexes by TGA/DTG (thermogravimetric/derivative thermogravimetric) indicates that complexes are stable upto 200 ºC temperature making them suitable for use in display devices. Analysis of the photophysical properties was carried out in both solid and solution states using PL (photoluminescence) studies, color parameters, J–O (Judd–Ofelt) analysis and bandgap. Most emissive transition (5D0 → 7F2) is responsible for the red emission in the complexes. The CIE (Commission International de I’Eclairage) coordinates of complexes also indicate the red emission on UV excitation. The bandgap which was obtained in the range of 2.54–3.02 eV reveals the semiconducting behavior of complexes. Values of J–O parameters and Ω2 in the complexes reflect asymmetric chemical environment around Eu (III) and less covalence and the Ω4 indicates that complexes are less rigid. Bandgap calculated through DFT (density function theory) for complexes is in range of 2.37–2.77 eV, and intensity parameters (J–O), energy transfer rates, and spherical coordinates were determined by LUMPAC software. The computational data are in good harmony with the experimental data. Further biological aspects of complexes were studied using antioxidant and antimicrobial studies.

Graphical abstract

为了探索 Eu(III)在显示器和光电子学中的应用,我们合成了六种以β-羟基酮为配体、含杂环化合物为辅助配体的红光发光 Eu(III)配合物。通过傅立叶变换红外光谱(FTIR)、核磁共振(1H-NMR)和 13C-NMR 等多种技术确定了配体和辅助配体与 Eu(III)离子的配位行为。通过 XRD(X 射线衍射)、SEM(扫描电子显微镜)和 EDS(能量色散 X 射线光谱)分析研究了络合物的形态和纯度,结果表明络合物呈半晶体状且纯净。通过 TGA/DTG(热重/衍生热重)对络合物进行的热分析表明,络合物在高达 200 ºC 的温度下都很稳定,因此适合用于显示设备。利用 PL(光致发光)研究、颜色参数、J-O(Judd-Ofelt)分析和带隙,对固态和溶液态的光物理特性进行了分析。大多数发射转变(5D0 → 7F2)是复合物发出红色光的原因。复合物的 CIE(国际照明委员会)坐标也表明,在紫外线激发下会发出红色光。在 2.54-3.02 eV 范围内获得的带隙显示了配合物的半导体行为。络合物中的 J-O 参数值和 Ω2 值反映了 Eu (III) 周围不对称的化学环境和较少的共价性,而 Ω4 则表明络合物的刚性较低。通过 DFT(密度函数理论)计算出的配合物带隙范围为 2.37-2.77 eV,并通过 LUMPAC 软件确定了强度参数(J-O)、能量传递率和球面坐标。计算数据与实验数据十分吻合。利用抗氧化和抗菌研究对复合物的生物学方面进行了进一步研究。
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Photochemical & Photobiological Sciences
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