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Photoacoustic lifetime oxygen imaging of radiotherapy-induced tumor reoxygenation In Vivo 放疗诱导的肿瘤体内复氧的光声寿命氧成像
IF 3.261 Pub Date : 2024-04-27 DOI: 10.1016/j.jpap.2024.100241
Jeff Folz , Janggun Jo , Maria E. Gonzalez , Ahmad Eido , Tianqu Zhai , Roberta Caruso , Celina G. Kleer , Xueding Wang , Raoul Kopelman

Purpose

Early detection and diagnosis of cancer is critical for achieving positive therapeutic outcomes. Biomarkers that can provide clinicians with clues to the outcome of a given therapeutic course are highly desired. Oxygen is a small molecule that is nearly universally present in biological tissues and plays a critical role in the effectiveness of radiotherapies by reacting with DNA radicals and subsequently impairing cellular repair of double strand breaks.

Techniques for measuring oxygen in biological tissues often use blood oxygen saturation to approximate the oxygen partial pressure in surrounding tissues despite the complex, nonlinear, and dynamic relationship between these two separate oxygen populations.

Methods and materials

We combined a directly oxygen-sensitive, tumor-targeted, chemical contrast nanoelement with the photoacoustic lifetime-based (PALT) oxygen imaging technique to obtain image maps of oxygen in breast cancer tumors in vivo. The oxygen levels of patient-derived xenografts in a mouse model were characterized before and after a course of radiotherapy.

Results

We show that, independent of tumor size, radiotherapy induced an increase in the overall oxygenation levels of the tumor. Further, this increase in the oxygenation of the tumor significantly correlated with a positive response to radiotherapy, as demonstrated by a reduction in tumor volume over the twenty-day monitoring period following therapy and histological staining.

Conclusion

Our PALT imaging presented here is simple, fast, and non-invasive. Facilized by the PALT approach, imaging of tumor reoxygenation may be utilized as a simple, early indicator for evaluating cancer response to radiotherapy. Further characterization of the reoxygenation degree, temporal onset, and possible theragnostic implications are warranted.

目的癌症的早期检测和诊断对于取得积极的治疗效果至关重要。能够为临床医生提供特定疗程结果线索的生物标记物是非常需要的。氧是一种几乎普遍存在于生物组织中的小分子,它能与 DNA 自由基发生反应,进而影响细胞对双链断裂的修复,因此对放射治疗的效果起着至关重要的作用。测量生物组织中氧含量的技术通常使用血氧饱和度来近似测量周围组织中的氧分压,尽管这两种不同的氧含量之间存在着复杂、非线性和动态的关系。方法与材料我们将一种直接对氧敏感的肿瘤靶向化学对比纳米元素与基于光声寿命(PALT)的氧成像技术相结合,获得了体内乳腺癌肿瘤中氧含量的图像图。结果表明,与肿瘤大小无关,放疗会引起肿瘤整体氧含量的增加。此外,肿瘤氧合水平的提高与放疗的积极反应密切相关,放疗后二十天监测期内肿瘤体积的缩小和组织学染色证明了这一点。通过 PALT 方法,肿瘤复氧成像可作为评估癌症对放疗反应的一个简单、早期指标。我们有必要对复氧程度、时间起始和可能的治疗意义进行进一步的描述。
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引用次数: 0
Polyaniline-supported g-C3N4/ZnO/Ag2CrO4 composite for photodegradation of methylene blue under visible light irradiation 聚苯胺支撑的 g-C3N4/ZnO/Ag2CrO4 复合材料在可见光照射下对亚甲基蓝的光降解作用
IF 3.261 Pub Date : 2024-04-23 DOI: 10.1016/j.jpap.2024.100239
Ziyad Abrahim, Abi M. Taddesse, Yiheyis Bogale, Zewdu Bezu, Endale Teju

Organic dyes are a major source of environmental pollution from different industries. To remove these recalcitrant, a novel ternary g-C3N4/ZnO/Ag2CrO4 and its polyaniline-supported (PANI) composites were synthesized using an “in situ” oxidative polymerization approach. XRD, SEM, UV–Vis DRS, and PL techniques were utilized to characterize the as-prepared composites. The photocatalytic efficiency was evaluated using a model organic pollutant, methylene blue (MB), and samples of the effluent of the textile industry. The as-synthesized ternary g-C3N4/ZnO/Ag2CrO4 (ZT3= 87.87 %) composite showed better photocatalytic performance than the single (5 %) and binaries (15–25 %) counterparts for MB degradation. The influence of various experimental settings on the photodegradation of MB dye was examined and these were an initial dye amount of 10 ppm, photocatalyst load of 0.15 g/L, and pH 10. Under optimized conditions, PANI-supported g-C3N4/ZnO/Ag2CrO4 composite (PAST) demonstrated substantial degradation efficiency (97.5 %). The reusability study of the spent catalyst revealed a reduced efficiency from 97.5 to 78.5 % photodegradation of MB after four successive cycles, demonstrating the photocatalyst's stability and efficiency. According to the study on the effect of scavengers, h+ plays a significant part in the discoloration of MB. The PAST photocatalyst outperformed the MB discoloration (97.5 %) and adequate degradation for real textile effluent samples (77.7 %) collected from Hawassa textile industries. The photodegradation efficiency result of this study demonstrated that PANI-supported g-C3N4/ZnO/Ag2CrO4 might serve as an advantageous photocatalyst for the efficient removal of MB and other dyes under visible light irradiation at the optimum conditions. The total estimated cost analysis of synthesis and photocatalytic degradation using Polyaniline-supported g-C3N4/ZnO/Ag2CrO4 composite found that it was quite affordable, costing around $5 per 1,000 L of wastewater treatment.

有机染料是不同工业的主要环境污染源。为了去除这些难降解的有机染料,研究人员采用 "原位 "氧化聚合方法合成了新型三元 g-C3N4/ZnO/Ag2CrO4 及其聚苯胺支撑(PANI)复合材料。利用 XRD、SEM、UV-Vis DRS 和 PL 技术对制备的复合材料进行了表征。光催化效率的评估采用了一种示范有机污染物亚甲基蓝(MB)和纺织工业废水样品。在降解甲基溴方面,合成的三元 g-C3N4/ZnO/Ag2CrO4 (ZT3= 87.87 %)复合材料的光催化性能优于单元(5 %)和双元(15-25 %)复合材料。研究了各种实验设置对甲基溴染料光降解的影响,包括初始染料量为 10 ppm、光催化剂负载量为 0.15 g/L、pH 值为 10。在优化条件下,PANI 支持的 g-C3N4/ZnO/Ag2CrO4 复合材料(PAST)表现出了很高的降解效率(97.5%)。对废催化剂的可再利用性研究表明,经过四个连续循环后,甲基溴的光降解效率从 97.5% 降至 78.5%,这证明了光催化剂的稳定性和效率。根据对清除剂影响的研究,h+ 对甲基溴的褪色起着重要作用。PAST 光催化剂在甲基溴褪色(97.5%)和充分降解从 Hawassa 纺织业收集的实际纺织污水样品(77.7%)方面表现优异。这项研究的光降解效率结果表明,在最佳条件下,PANI 支持的 g-C3N4/ZnO/Ag2CrO4 可以作为一种有利的光催化剂,在可见光照射下高效去除甲基溴和其他染料。使用聚苯胺支撑的 g-C3N4/ZnO/Ag2CrO4 复合材料进行合成和光催化降解的总成本估算分析表明,其成本相当低廉,每 1,000 升废水的处理成本约为 5 美元。
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引用次数: 0
Solution conductivity as a factor determining the photocatalytic reaction rate 溶液电导率是决定光催化反应速率的一个因素
IF 3.261 Pub Date : 2024-04-23 DOI: 10.1016/j.jpap.2024.100240
E. Lilov , S. Nedev , V. Lilova , S. Kozhukharov , Ch. Girginov

A rather simple model was developed, which predicted a hyperbolic relation between the photocatalytic reaction rate and solution conductivity. Experimental validation was performed using methyl orange as a model pollutant and titanium dioxide as a photocatalyst. The experiments, conducted with three different salts confirm the hyperbolic correlation between the photocatalytic degradation rate and solution conductivity. The results have evinced this correlation, albeit the model ignores crucial factors, such as the role of one of the two types of charges generated during light absorption and the chemical decomposition pathway. In addition, the experimentally derived hyperbolic function displays a positive shift along the ordinate.

建立了一个相当简单的模型,该模型预测光催化反应速率与溶液电导率之间存在双曲线关系。以甲基橙为模型污染物,二氧化钛为光催化剂,进行了实验验证。使用三种不同盐类进行的实验证实了光催化降解率与溶液电导率之间的双曲线关系。尽管模型忽略了一些关键因素,例如光吸收过程中产生的两种电荷之一的作用和化学分解途径,但实验结果证明了这种相关性。此外,实验得出的双曲线函数显示出沿纵坐标的正向移动。
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引用次数: 0
Advances in exploration of photoinduced electron transfer reactions involving small molecules probed by magnetic field effect 利用磁场效应探测涉及小分子的光诱导电子转移反应的探索进展
IF 3.261 Pub Date : 2024-03-30 DOI: 10.1016/j.jpap.2024.100238
Brotati Chakraborty , Chaitrali Sengupta , Samita Basu

The review focuses on photoinduced electron transfer (PET) reactions between small molecules and various kinds of chemical and biological systems using a weak external magnetic field (MF). Laser flash photolysis is a competent tool to characterize the intermediates which are formed due to PET. A weak MF, very close to the hyperfine interaction of the system, has the potential to inhibit or enhance reaction channels for singlet and triplet states, which eventually effects the product distribution. At first, well-documented examples of PET involving small molecules like derivatives of phenazines, carbazoles and acridines with classical electron donors in varying homogeneous and heterogeneous media have been discussed and the influence of a weak MF on the dynamics of PET is highlighted. Secondly, utilization of magnetic field effect (MFE) to probe PET in protein pockets has been described. Thirdly, an extensive discussion on PET involving nucleobases, nucleosides, nucleotides and nucleic acids and subsequent MFE on such reactions has been reported. Next, MFE has been exploited to study PET involving nanomaterials. Finally, some very recent studies of MFE have been discussed. Thus, this review is an attempt to unravel various aspects of PET in a large number of systems of varying dimensions by means of several facets of MFE like B1/2 parameter, its capability to authenticate the initial spin state and distance dependence property.

这篇综述侧重于利用弱外部磁场(MF)在小分子与各种化学和生物系统之间进行光诱导电子转移(PET)反应。激光闪烁光解是表征 PET 形成的中间产物的有效工具。非常接近系统超频相互作用的弱磁场有可能抑制或增强单线态和三线态的反应通道,最终影响产物的分布。首先,讨论了在不同的均相和异相介质中,涉及小分子(如吩嗪、咔唑和吖啶的衍生物)与经典电子供体的 PET 的有据可查的实例,并强调了弱 MF 对 PET 动态的影响。其次,介绍了利用磁场效应(MFE)探测蛋白质口袋中 PET 的情况。第三,报告广泛讨论了涉及核碱基、核苷、核苷酸和核酸的 PET 以及随后对此类反应的磁场效应。接着,利用 MFE 研究了涉及纳米材料的 PET。最后,还讨论了一些最新的 MFE 研究。因此,本综述试图通过 MFE 的几个方面(如 B1/2 参数、验证初始自旋态的能力和距离依赖性)来揭示大量不同维度系统中 PET 的各个方面。
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引用次数: 0
Addressing the competing adsorption bottleneck in photoreduction of CO2 using a hydrophilic-hydrophobic heterojunction photocatalyst 利用亲水-疏水异质结光催化剂解决二氧化碳光还原过程中的竞争吸附瓶颈问题
IF 3.261 Pub Date : 2024-03-15 DOI: 10.1016/j.jpap.2024.100236
Ragulkrishnan V , Tarek Fawzi , Subbiah Alwarappan , Tiju Thomas , Hyeonseok Lee , Somnath C Roy

Solar powered conversion / reduction of carbon dioxide into value added chemicals has been identified as one of the foremost challenges for materials science in the 21st century. Despite extensive research, product yield remained low and one of the primary factors has been the issue of competing adsorption of CO2 and water vapour on the catalyst surface. In this work we employ reduced graphene oxide wrapped TiO2 nanotubes (TiO2 - rGO) as a heterojunction photocatalyst and demonstrate that UV irradiation induces hydrophilicity on the TiO2 surface and, hydrophobicity on the rGO surface. The resulting photocatalyst shows 25 % higher yield of methane over that of untreated photocatalyst. Hence, UV irradiation induced tailoring of the hydrophilicity yields selective adsorption sites for the CO2 and water vapour leading to a significant enhancement of the methane yield through photocatalytic reduction process.

利用太阳能将二氧化碳转化/还原为高附加值化学品已被确定为 21 世纪材料科学面临的首要挑战之一。尽管进行了大量研究,但产品产量仍然很低,其中一个主要因素是催化剂表面对二氧化碳和水蒸气的竞争吸附问题。在这项工作中,我们采用还原氧化石墨烯包裹的二氧化钛纳米管(TiO2 - rGO)作为异质结光催化剂,并证明紫外线照射可诱导二氧化钛表面的亲水性和 rGO 表面的疏水性。与未经处理的光催化剂相比,这种光催化剂的甲烷产率提高了 25%。因此,紫外线照射引起的亲水性定制产生了二氧化碳和水蒸气的选择性吸附位点,从而通过光催化还原过程显著提高了甲烷产量。
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引用次数: 0
Eggshell microstructure, shell quality indices, mineralogy, and UV–Vis absorbance of domestic eggs of Iran 伊朗家鸡蛋的蛋壳微观结构、蛋壳质量指数、矿物学和紫外可见吸收率
IF 3.261 Pub Date : 2024-03-07 DOI: 10.1016/j.jpap.2024.100235
M.B. Fathi , Z. Taghizadeh RahmatAbadi

The structure and quality of eggshells (ES) vary around a mean value depending on different items, and these variations are important in their many industrial and technological applications as will be mentioned (vide infra). Five commercial egg brands of different laying hens are examined and their quality indices, morphological microstructure, elemental composition, and light absorbance at 200–700 nm UV/Vis spectra were compared. The ES layers include a limiting membrane, inner and outer shell membranes, a mammillary layer, a palisade layer, a surface vertical crystal layer, and a bilayer cuticle. The elemental composition of each layer reflects the proteinous or calcified nature of the layers, and various elements, C, O, N, Ca, Fe, Mg, Mn, Pb, Sr, Sc, Hf, Co, and La, were found. The weight difference between egg brands was significant, as well as the difference in ES percentage between white and colored eggs. ES weight possessed a positive relationship with the thickness of the calcified layer. So, the ES is heavier and the egg is larger and heavier when the calcified layer is thicker. The calculated average ES index was 7.99% ± 0.16 SE. In all ES samples, the absorbance in UV wavelength spectra (300–350 nm) was slightly higher than in Vis spectra (400 - 700 nm) and their difference was significant. The difference in absorbance of various treatments was significant and mean absorbance was the highest in the after-furnace (ash) samples and was the lowest for acid-treated ones. It seems that turning the ES into ash can improve the absorbance capability, especially in white ESs.

蛋壳(ES)的结构和质量因不同项目而围绕平均值变化,这些变化在许多工业和技术应用中都很重要(参见下文)。对不同产蛋鸡产的五个商品鸡蛋品牌进行了研究,并比较了它们的质量指标、形态微观结构、元素组成和 200-700 纳米紫外/可见光谱吸光度。ES 层包括限制膜、外壳内膜和外壳外膜、乳腺层、腭层、表面垂直晶体层和双层角质层。各层的元素组成反映了各层的蛋白质或钙化性质,并发现了 C、O、N、Ca、Fe、Mg、Mn、Pb、Sr、Sc、Hf、Co 和 La 等多种元素。不同品牌鸡蛋的重量差异显著,白壳蛋和彩蛋的 ES 百分比差异也显著。ES 重量与钙化层厚度呈正相关。因此,钙化层越厚,ES 就越重,鸡蛋也就越大和越重。计算得出的平均 ES 指数为 7.99% ± 0.16 SE。在所有 ES 样品中,紫外光谱(300-350 nm)的吸光度略高于可见光谱(400-700 nm),两者差异显著。各种处理方法的吸光度差异显著,炉后(灰烬)样品的平均吸光度最高,酸处理样品的平均吸光度最低。由此看来,将 ES 变成灰烬可以提高吸光能力,尤其是白色 ES 的吸光能力。
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引用次数: 0
Estimating population-level 25-hydroxyvitamin D concentrations in Australia and New Zealand using the sun exposure (SUNEX) microsimulation model 利用阳光照射(SUNEX)微观模拟模型估算澳大利亚和新西兰人口中 25-羟基维生素 D 的浓度
IF 3.261 Pub Date : 2024-03-02 DOI: 10.1016/j.jpap.2024.100234
Thomas M. Elliott , Rachel E. Neale , Anna Foeglein , Ann Webb , Jonathan Karnon , Ian R. Reid , Craig Sinclair , Tracy Comans , Karen van Gorp , Vanessa Fanning , Louisa G. Gordon

Exposure to ultraviolet (UV) radiation from the sun has both harms and benefits for human health. The best-known benefit of sun exposure is the generation of vitamin D within the skin and the best-known harm is malignant skin cancer. Australia and New Zealand have very high ambient UV radiation, resulting in high rates of skin cancer incidence and mortality, yet there is an appreciable prevalence of vitamin D deficiency (defined as blood 25-hydroxyvitamin D (25(OH)D) < 50 nmol/L) in both populations. The purpose of this study was to create a microsimulation model to replicate population 25(OH)D concentrations of people living in Australia and New Zealand, thus enabling the effect of different population-wide interventions to be estimated. We used large population datasets containing data on sun behaviours and socio-demographic variables, and environmental data on UV radiation, ozone, and solar zenith angle. Latitude, weather and time of day were accounted for. We simulated the conversion of daily UV radiation to a standard vitamin D dose (SDD) (100 J/m2 vitamin D-weighted UV) and monthly accumulation of SDD to 25(OH)D concentration. The model was calibrated to match the seasonal prevalence of vitamin D deficiency. This report describes the Sun Exposure (SUNEX) microsimulation model, its development, data inputs and calibration against population prevalence of vitamin D deficiency.

阳光中的紫外线(UV)辐射对人体健康有百害而无一利。晒太阳最广为人知的好处是在皮肤中生成维生素 D,而最广为人知的危害则是恶性皮肤癌。澳大利亚和新西兰的环境紫外线辐射量非常高,因此皮肤癌的发病率和死亡率都很高,但这两个国家的人口中维生素 D 缺乏症(定义为血液中 25- 羟基维生素 D (25(OH)D) < 50 nmol/L)的发病率却很高。本研究的目的是创建一个微观模拟模型,以复制澳大利亚和新西兰人口的 25(OH)D 浓度,从而估算不同的全民干预措施的效果。我们使用了包含晒太阳行为和社会人口变量数据以及紫外线辐射、臭氧和太阳天顶角环境数据的大型人口数据集。纬度、天气和一天中的时间都考虑在内。我们模拟了将每日紫外线辐射量转换为标准维生素 D 剂量(SDD)(100 J/m2 维生素 D 加权紫外线)以及将每月累积的 SDD 转换为 25(OH)D 浓度的过程。该模型经过校准,以符合维生素 D 缺乏症的季节流行率。本报告介绍了太阳暴露(SUNEX)微观模拟模型、其开发、数据输入以及根据维生素 D 缺乏症的人群流行率进行的校准。
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引用次数: 0
Solvent selection for anthrocyanin dye extraction from Kigelia Africana and Hibiscus sabdariffa for dye sensitized solar cells 染料敏化太阳能电池从非洲木槿和木槿中提取蒽氰染料的溶剂选择
IF 3.261 Pub Date : 2024-02-22 DOI: 10.1016/j.jpap.2024.100233
T. Satish Kumar , S. Shalini , T. Anurag Roy , S. Prasanna , R. Balasundaraprabhu , Senthilarasu Sundaram

The main flavonoid pigment in the petals of Kigelia Africana and the calyx of Hibiscus sabdariffa is anthocyanin, responsible for the vibrant red, maroon, and purple hues in flowers. This pigment can modulate incident light on flowers, prompting its selection for detailed investigation. TiO2 nanostructures were synthesized using a one-step hydrothermal method, revealing the formation of nanorods and a single-phase rutile structure through FESEM and XRD analyses, respectively. The study aimed to assess the impact of various solvents on the extraction of natural dyes, which were subsequently sensitized on TiO2 photoanodes for DSSC applications. Four solvents-water, water with HCl, ethanol, and citric acid were employed to extract natural dyes from Kigelia Africana's petals and Hibiscus sabdariffa's calyx. Notably, dyes extracted with citric acid demonstrated promising results. The conversion efficiency of DSSCs fabricated with Kigelia Africana dye and Hibiscus sabdariffa dye, extracted using citric acid as the solvent, was found to be 0.87 % and 0.92 %, respectively. The implications of these findings are discussed.

非洲鸢尾(Kigelia Africana)花瓣和木槿(Hibiscus sabdariffa)花萼中的主要类黄酮色素是花青素,它能使花朵呈现出鲜艳的红色、褐红色和紫色。这种色素可以调节花朵上的入射光,因此被选中进行详细研究。研究人员采用一步水热法合成了 TiO2 纳米结构,并通过 FESEM 和 XRD 分析分别揭示了纳米棒和单相金红石结构的形成。该研究旨在评估各种溶剂对天然染料萃取的影响,然后将天然染料敏化在 TiO2 光阳极上,用于 DSSC 应用。研究采用了四种溶剂--水、含盐酸的水、乙醇和柠檬酸--从非洲鸢尾(Kigelia Africana)花瓣和木槿(Hibiscus sabdariffa)花萼中提取天然染料。值得注意的是,用柠檬酸提取的染料显示出良好的效果。使用柠檬酸作为溶剂萃取的非洲木槿染料和芙蓉染料制造的 DSSC 转换效率分别为 0.87 % 和 0.92 %。本文讨论了这些发现的意义。
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引用次数: 0
Fenton-mediated solar-driven photocatalysis of industrial dye effluent with polyaniline impregnated with activated TiO2-Nps 用浸渍了活性 TiO2-Nps 的聚苯胺对工业染料废水进行 Fenton 介导的太阳能光催化处理
IF 3.261 Pub Date : 2024-02-07 DOI: 10.1016/j.jpap.2024.100231
Joshua Akinropo Oyetade, Revocatus Lazaro Machunda, Askwar Hilonga

Various integrated technologies have been investigated for the remediation of heavily polluted industrial dye effluent. Also, more than 70 % of these dyes are known to be solely azo dyes used in the textile industry with 5–30 % presence in the effluent as loose dye molecules which are recalcitrant to treatment. These challenges led to the investigation of energy-efficient processes (solar) and the fabrication of high-performance nano-photocatalysts for proficient photocatalysis of dye effluent while mediating the process with Fenton reagents. The study fabricated nanopolymeric catalyst composites (P-AKT) via novel in situ coupling and impregnation of the polyaniline (PANI) with surface-activated TiO2 NPs. This fabrication is aimed at developing a high-performance catalyst with rapid and proficient photocatalytic activities to photons from sunlight irradiation. The photocatalytic process was mediated using a novel Fenton reagent to enhance the generation of radical species for dye degradation. Various instrumental characterization methods were used to study the structural, molecular, elemental, functional and optoelectronic properties of the fabricated nanocomposite photocatalysts. The result reveals functional groups aiding dye-catalyst bonding and morphological interaction reveal a surface-activated tetragonal crystalline mixture of anatase and rutile from TiO2Nps embedded in the macromolecular chain of PANI. It also reveals the optimal conditions of 20 mg dosage, 10 mg/L initial concentration with substantial effectiveness at pH of 5 and 7. However, the most efficient photocatalyst recorded was P-AKT-2 % and P-AKT-3 % having 95 % and 94 % efficiencies at 90 min of solar irradiation. The photocatalyst equally demonstrated its capacity for effluent treatability up to 4 cycles of use.

为治理污染严重的工业染料废水,人们研究了各种综合技术。此外,已知这些染料中有 70% 以上完全是纺织工业中使用的偶氮染料,其中 5-30% 以松散染料分子的形式存在于废水中,这些染料对处理具有顽抗性。这些挑战促使人们对节能工艺(太阳能)进行研究,并制造出高性能纳米光催化剂,用于染料废水的高效光催化,同时利用芬顿试剂对该工艺进行调解。该研究通过聚苯胺(PANI)与表面活性 TiO2 NPs 的新型原位耦合和浸渍,制备了纳米多聚物催化剂复合材料(P-AKT)。这种制备方法旨在开发一种高性能催化剂,它对来自太阳光照射的光子具有快速、高效的光催化活性。光催化过程使用新型 Fenton 试剂来促进染料降解自由基的生成。利用各种仪器表征方法研究了所制备纳米复合光催化剂的结构、分子、元素、功能和光电特性。结果表明,功能基团有助于染料与催化剂的结合,而形态相互作用则揭示了嵌入 PANI 大分子链中的 TiO2-Nps 的锐钛矿和金红石的表面活性四方晶体混合物。研究还揭示了 20 毫克用量、10 毫克/升初始浓度的最佳条件,在 pH 值为 5 和 7 时具有显著效果。然而,最有效的光催化剂是 P-AKT-2 % 和 P-AKT-3%,在太阳光照射 90 分钟时的效率分别为 95 % 和 94 %。这种光催化剂同样显示了其污水处理能力,可使用 4 个周期。
{"title":"Fenton-mediated solar-driven photocatalysis of industrial dye effluent with polyaniline impregnated with activated TiO2-Nps","authors":"Joshua Akinropo Oyetade,&nbsp;Revocatus Lazaro Machunda,&nbsp;Askwar Hilonga","doi":"10.1016/j.jpap.2024.100231","DOIUrl":"https://doi.org/10.1016/j.jpap.2024.100231","url":null,"abstract":"<div><p>Various integrated technologies have been investigated for the remediation of heavily polluted industrial dye effluent. Also, more than 70 % of these dyes are known to be solely azo dyes used in the textile industry with 5–30 % presence in the effluent as loose dye molecules which are recalcitrant to treatment. These challenges led to the investigation of energy-efficient processes (solar) and the fabrication of high-performance nano-photocatalysts for proficient photocatalysis of dye effluent while mediating the process with Fenton reagents. The study fabricated nanopolymeric catalyst composites (P-AKT) via novel in situ coupling and impregnation of the polyaniline (PANI) with surface-activated TiO<sub>2</sub> NPs. This fabrication is aimed at developing a high-performance catalyst with rapid and proficient photocatalytic activities to photons from sunlight irradiation. The photocatalytic process was mediated using a novel Fenton reagent to enhance the generation of radical species for dye degradation. Various instrumental characterization methods were used to study the structural, molecular, elemental, functional and optoelectronic properties of the fabricated nanocomposite photocatalysts. The result reveals functional groups aiding dye-catalyst bonding and morphological interaction reveal a surface-activated tetragonal crystalline mixture of anatase and rutile from TiO<sub>2</sub><sup>−</sup>Nps embedded in the macromolecular chain of PANI. It also reveals the optimal conditions of 20 mg dosage, 10 mg/L initial concentration with substantial effectiveness at pH of 5 and 7. However, the most efficient photocatalyst recorded was P-AKT-2 % and P-AKT-3 % having 95 % and 94 % efficiencies at 90 min of solar irradiation. The photocatalyst equally demonstrated its capacity for effluent treatability up to 4 cycles of use.</p></div>","PeriodicalId":375,"journal":{"name":"Journal of Photochemistry and Photobiology","volume":"20 ","pages":"Article 100231"},"PeriodicalIF":3.261,"publicationDate":"2024-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S266646902400006X/pdfft?md5=119aef62ae1dca5af9eef5d61898deff&pid=1-s2.0-S266646902400006X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139731594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Development of a red-shifted photosensitizer for near-infrared photoimmunotherapy of cancer 开发用于癌症近红外光免疫疗法的红移光敏剂
IF 3.261 Pub Date : 2024-02-05 DOI: 10.1016/j.jpap.2024.100230
Yuto Goto , Kanta Ando , Hideo Takakura , Kohei Nakajima , Masato Kobayashi , Osamu Inanami , Tetsuya Taketsugu , Mikako Ogawa

Near-infrared photoimmunotherapy (NIR-PIT) is a recently described method for cancer treatment that utilizes an antibody-conjugated phthalocyanine photosensitizer and NIR light. In NIR-PIT, light of 690 nm wavelength is used to activate a photosensitizer, IR700, while longer-wavelength light penetrates deeper into tissues. Thus, more effective NIR-PIT would be achieved by using photosensitizers that are activated by longer-wavelength light. The absorption wavelength would be red-shifted by destabilizing the highest occupied molecular orbital (HOMO) energy level by introducing electron donating groups at the α positions of a phthalocyanine ring. In this study, we developed a red-shifted photosensitizer for NIR-PIT, KA800, whose absorption wavelength was red-shifted by the introduction of ethoxy groups to IR700. As intended, the absorption maximum of KA800 was red-shifted compared to IR700 by 84 nm. Although phototoxicity of the antibody-KA800 (Ab-KA800) conjugate was observed in cultured cancer cells, no therapeutic effect was observed in mice. This is because the cytotoxicity of Ab-KA800 was mainly due to singlet oxygen, which can be quenched by abundant antioxidants in vivo. KA800 had low reactivity with respect to axial ligand cleavage required for inducing cell death via aggregate formation, a unique cytotoxic mechanism in NIR-PIT. The axial ligand cleavage proceeds via the anion radical formation of the photosensitizer, and KA800 was found to be less likely to receive an electron than IR700. This may be due to the destabilization of the HOMO energy level of KA800. Therefore, our findings suggest that stabilizing the lowest unoccupied molecular orbital (LUMO) energy level would be better than destabilizing the HOMO energy level for developing a red-shifted photosensitizer for NIR-PIT.

近红外光免疫疗法(NIR-PIT)是最近描述的一种利用抗体结合酞菁光敏剂和近红外光治疗癌症的方法。在近红外光免疫疗法中,波长为 690 纳米的光被用来激活光敏剂 IR700,而波长更长的光则能更深地穿透组织。因此,使用波长更长的光来激活光敏剂,可以实现更有效的近红外-PIT。通过在酞菁环的α位置引入电子捐赠基团,破坏最高占位分子轨道(HOMO)能级的稳定性,从而实现吸收波长的红移。在这项研究中,我们开发了一种用于近红外光敏剂的红移光敏剂 KA800,通过在 IR700 中引入乙氧基,其吸收波长发生了红移。正如预期的那样,与 IR700 相比,KA800 的吸收最大值红移了 84 nm。虽然在培养的癌细胞中观察到了抗体-KA800(Ab-KA800)共轭物的光毒性,但在小鼠体内没有观察到治疗效果。这是因为抗体-KA800 的细胞毒性主要是由单线态氧引起的,而单线态氧在体内可以被丰富的抗氧化剂淬灭。KA800 对通过聚集体形成诱导细胞死亡所需的轴配体裂解反应活性较低,而聚集体形成是 NIR-PIT 的独特细胞毒性机制。轴向配体裂解是通过光敏剂的阴离子自由基形成进行的,与 IR700 相比,KA800 得到电子的可能性较低。这可能是由于 KA800 的 HOMO 能级不稳定所致。因此,我们的研究结果表明,在开发用于近红外光敏剂的红移光敏剂时,稳定最低未占分子轨道(LUMO)能级比破坏 HOMO 能级的稳定性更好。
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引用次数: 0
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Journal of Photochemistry and Photobiology
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