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Photocatalytic conversion of copper (II) ions to metallic copper (0) on TiO2 nanoparticles. TiO2纳米颗粒上铜(II)离子光催化转化为金属铜(0)的研究。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-01 Epub Date: 2025-03-13 DOI: 10.1007/s43630-025-00702-1
Zhen-Kun He, Jiayin Xu, Qinzhuan Shu, Haobo Li, Zhina Ji, Aimin Liu, Haitao Huang, Zhongning Shi

Under the initiative of the United Nations Sustainable Development Goals (SDGs), utilization of clean energy for metallurgy has emerged as a new trend in recent years. Precious metal ions with low chemical reactivity have been readily photoreduced, while active metal such as copper has been rarely reported. In this work, photocatalytic reduction of Cu(II) ions was investigated utilizing TiO2 nanoparticles as catalyst. By surface charge optimization in different anionic species-based cupric solution, nanoparticle products with Cu2O as out shell and zero-valent Cu as the core have been photocatalytic prepared. The photocatalysis conditions such as catalyst amount, Cu(II) ions concentration, ethanol addition, and illumination wavelength were optimized, good cycling stability was confirmed. Argon etching results and thermogravimetric analysis confirmed the appearance of zero-valent Cu metal in the core of nanoparticle products. Ex situ photoreaction investigation revealed the consumption pathway of oxidative holes and photoreduction mechanism of Cu(II) ions. This research could provide some insights into the photoreduction method of active metals and the photocatalytic removal of heavy metal ions within the realm of environmental protection.

在联合国可持续发展目标(SDGs)的倡议下,近年来冶金清洁能源利用已成为一种新趋势。化学反应性较低的贵金属离子很容易被光还原,而活性金属如铜却很少被报道。本文以TiO2纳米颗粒为催化剂,研究了Cu(II)离子的光催化还原。通过在不同阴离子型铜溶液中进行表面电荷优化,制备了以Cu2O为外壳、零价Cu为核心的纳米颗粒产物。对催化剂用量、Cu(II)离子浓度、乙醇添加量、光照波长等光催化条件进行了优化,证实了该催化剂具有良好的循环稳定性。氩蚀结果和热重分析证实了纳米颗粒产品核心中存在零价铜金属。非原位光反应研究揭示了Cu(II)离子氧化孔的消耗途径和光还原机理。本研究可为环境保护领域中活性金属的光还原方法和重金属离子的光催化去除提供一些见解。
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引用次数: 0
Emerging role of ferroptosis in ultraviolet radiation-driven skin photoaging: a narrative review. 铁下垂在紫外线辐射驱动的皮肤光老化中的新作用:叙述性回顾。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-01 Epub Date: 2025-03-10 DOI: 10.1007/s43630-025-00691-1
Yan Teng, Youming Huang, Xiaohua Tao, Yibin Fan, Jianhua You

Photoaging is characterized by chronic inflammation in response to ultraviolet (UV) radiation. UV radiation causes skin cells to produce reactive oxygen species (ROS), which causes oxidative stress and inflammation. ROS can reversibly or irreversibly destroy different cellular compounds, including nucleic acids, proteins, free amino acids, lipids, lipoproteins, carbohydrates, and connective tissue macromolecules. Ferroptosis is a kind of programmed cell death caused by iron dependence and lipid peroxidation and has been recently discovered. Its occurrence is primarily related to iron metabolism, antioxidants, lipid peroxidation, and other processes. In addition, high levels of ROS can trigger oxidative stress, altering the redox balance within cells and thus initiating ferroptosis. Ferroptosis has been implicated in UV-driven skin photoaging. Moreover, UV radiation from sunlight can regulate numerous ferroptosis-linked genes. This review will focus on the function of ferroptosis in UV radiation-damaged skin cells. We hope to draw attention to the significance of ferroptosis regulation in the prevention and treatment of skin photoaging.

光老化的特征是对紫外线(UV)辐射的慢性炎症反应。紫外线辐射会导致皮肤细胞产生活性氧(ROS),从而导致氧化应激和炎症。ROS可以可逆或不可逆地破坏不同的细胞化合物,包括核酸、蛋白质、游离氨基酸、脂质、脂蛋白、碳水化合物和结缔组织大分子。铁中毒是近年来发现的一种由铁依赖和脂质过氧化引起的细胞程序性死亡。其发生主要与铁代谢、抗氧化剂、脂质过氧化等过程有关。此外,高水平的ROS可引发氧化应激,改变细胞内的氧化还原平衡,从而引发铁下垂。上睑下垂与紫外线驱动的皮肤光老化有关。此外,来自阳光的紫外线辐射可以调节许多与死铁有关的基因。本文就铁下垂在紫外线损伤皮肤细胞中的作用作一综述。我们希望引起人们对铁下垂调控在预防和治疗皮肤光老化中的重要意义的重视。
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引用次数: 0
Pt-doped g-C3N4 photocatalyst for simultaneous hydrogen production and value-added chemical synthesis under visible light. 可见光下同时产氢和增值化学合成的掺杂pt g-C3N4光催化剂。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-02-20 DOI: 10.1007/s43630-025-00683-1
Marwa Moussa, Abdessalem Hamrouni, Nawres Lazaar, Mounir Ferhi, Ichraf Chérif, Hinda Lachheb, Cláudia G Silva, Maria J Sampaio, Joaquim L Faria

Metal-free photocatalysts, especially through the use of semi-conductors g-C3N4 (graphitic carbon nitride, CN) have become a prominent topic due to their sustainable advantages and promising effectiveness in hydrogen (H2) production. However, CN material requires specific modifications, since its efficacy under visible light suffers from fast recombination of electron/hole pairs (e/h+), slow charge transfer and limited surface area. In this study, we present the synthesis of CN via the thermal treatment of urea and melamine mixture. To enhance its crystallinity and photocatalytic performance, Pt nanoparticles were loaded onto CN by simple incipient wetness impregnation method. The H2 production was investigated through the potential application of aromatic alcohols including anisyl (AA), benzyl (BA), piperonol (PA), and methanol (M) alcohols, as sacrificial reagents. H2 production was achieved using the hybrid Pt-CN system with the added benefit of value-added organic synthesis under visible light exposure. The Pt-CN photocatalyst exhibited varying H2 evolution rates on the alcohol used as sacrificial reagent, with the PA yielding to the highest rate of 503.5 µmol·g-1·h-1. Stability assessments confirmed the robustness of the synthesized Pt-CN photocatalyst across three consecutive visible light driven experiments. Notably, piperonal (P) synthesis occurred along with H2 production under visible light. Comprehensive structural, textural, morphologic, optoelectronic and electrochemical characterizations were performed correlating the Pt-CN's properties with its visible photocatalytic performance.

无金属光催化剂,特别是通过使用半导体的g-C3N4(石墨化碳氮,CN)由于其可持续的优势和在氢(H2)生产中有前景的有效性而成为一个突出的话题。然而,CN材料需要特定的修饰,因为它在可见光下的效率受到电子/空穴对(e - /h+)快速重组、电荷转移缓慢和表面积有限的影响。在本研究中,我们介绍了尿素和三聚氰胺混合物的热处理合成CN。为了提高其结晶度和光催化性能,采用简单的初始湿浸渍法将Pt纳米颗粒负载到CN上。以茴香基(AA)、苄基(BA)、胡椒醇(PA)和甲醇(M)醇为牺牲剂,研究了其产氢的潜在应用。利用Pt-CN混合体系实现了制氢,并在可见光下进行了增值有机合成。Pt-CN光催化剂对牺牲试剂乙醇的析氢速率不同,其中PA的最高收率为503.5µmol·g-1·h-1。稳定性评估通过三个连续的可见光驱动实验证实了合成的Pt-CN光催化剂的稳健性。值得注意的是,在可见光下,辣椒醛(P)的合成伴随着H2的生成。对Pt-CN的结构、织构、形貌、光电和电化学性能进行了全面表征,并将其与可见光催化性能进行了对比。
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引用次数: 0
Photophysical and thermodynamic landscape of interaction of a styryl-based dye with DNA duplex: effect of medium ionic strength and live cell imaging. 苯乙烯基染料与DNA双工相互作用的光物理和热力学景观:介质离子强度和活细胞成像的影响。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-02-25 DOI: 10.1007/s43630-025-00693-z
Viki Bhakta, Zofa Shireen, SanjitDey, Bijan K Paul, Nikhil Guchhait

A red-emitting excited-state intramolecular charge transfer pyridinium dye, [4-((1E,3E)-4-(4-(dimethylamino)phenyl)buta-1,3-dien-1-yl)-1-methylpyridin-1-ium] (DAPBMP), was synthesized and characterized using NMR and ESIMS studies. Binding interaction between dye DAPBMP and genomic DNA were investigated using steady-state and time-resolved spectroscopic methods. The thermodynamics of the interaction process were characterized using isothermal titration calorimetry (ITC) which reveals the key role of the hydrophobic effect and electrostatic interaction between the positive charged dye and the negatively charged polyphosphate of DNA backbone. The binding of dye to the minor groove of the DNA double helix is confirmed by circular dichroism spectroscopy and molecular docking simulation study. The binding interaction is found to be strongly dependent on the ionic strength of the medium as demonstrated by a systematic study in the presence of various concentrations of NaCl. A detailed calorimetric study shows that polyelectrolytic contribution, ΔGpe, (a measure of the role of electrostatic force) to the total free energy change (ΔG) of interaction progressively decreases with increasing ionic strength of the medium due to weakening of the DAPBMP:DNA binding by screening of the electrostatic charges. The fluorescence of DAPBMP exhibits a remarkable emission enhancement of almost 15 times when the viscosity of the water-propylene glycol system increases. Fluorescent microscopy was performed with C2C12 mouse skeletal myoblast and A549 lung cancer cells in the presence of DAPBMP dye. The dye passed through the C2C12 cell membrane and binds the negatively charged nucleic acids, essentially double-stranded DNA which made the nuclear puncta along with perinuclear located mitochondria.

合成了一种发红光的分子内电荷转移吡啶染料[4-((1E,3E)-4-(4-(二甲氨基)苯基)丁-1,3-二烯-1-基)-1-甲基吡啶-1-ium] (DAPBMP),并用NMR和ESIMS对其进行了表征。利用稳态和时间分辨光谱方法研究染料DAPBMP与基因组DNA的结合相互作用。采用等温滴定量热法(ITC)对相互作用过程进行了热力学表征,揭示了带正电的染料与带负电的DNA主链聚磷酸盐之间的疏水效应和静电相互作用的关键作用。通过圆二色光谱和分子对接模拟研究证实了染料与DNA双螺旋小凹槽的结合。在不同浓度NaCl存在下的系统研究表明,结合相互作用强烈依赖于介质的离子强度。一项详细的量热研究表明,随着介质离子强度的增加,由于筛选静电荷削弱了DAPBMP:DNA结合,聚电解质对相互作用总自由能变化(ΔG)的贡献ΔGpe(一种静电力作用的测量)逐渐减少。当水-丙二醇体系的黏度增加时,DAPBMP的荧光发射增强了近15倍。在DAPBMP染料存在下,对C2C12小鼠骨骼肌母细胞和A549肺癌细胞进行荧光显微镜观察。染料穿过C2C12细胞膜,结合带负电荷的核酸,本质上是双链DNA,形成核点和核周线粒体。
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引用次数: 0
Xanthomonas campestris pv. campestris regulates virulence mechanisms by sensing blue light. 油菜黄单胞菌。Campestris通过感应蓝光调节毒力机制。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-02-24 DOI: 10.1007/s43630-025-00694-y
V P Conforte, J Rinaldi, H R Bonomi, A Festa, D Garacoche, S Foscaldi, E Castagnaro, A A Vojnov, F Malamud

Light is an environmental stimulus to which all living organisms are exposed. Numerous studies have shown that bacteria can modulate virulence factors through photoreceptor proteins. Xanthomonas campestris pv. campestris (Xcc) is the causative agent of the systemic vascular disease black rot, which affects cruciferous crops worldwide. Typical symptoms include V-shaped yellow lesions emanating from the leaf margins and blackening of the leaf veins. In previous work, we have shown that Xcc possesses a functional bacteriophytochrome (XccBphP) that regulates its virulence in response to red and far-red light. In addition to the XccBphP protein the Xcc genome codes for a blue light photoreceptor, a Light Oxygen Voltage (LOV) domain-containing protein with a histidine kinase (HK) as the output module. Here, we show that both photoreceptors are able to sense blue light. We demonstrated that XccLOV is a functional photoreceptor by performing loss and gain of function experiments with a knock-out and a complemented strain for the lov gene. Blue light negatively affected swimming motility, whereas xanthan production was regulated by XccBphP, in a blue light independent manner. Additionally, our studies showed that blue light altered biofilm structure patterns and enhanced virulence. Overall, these results revealed that some Xcc virulence factors are blue light modulated via at least two photoreceptors.

光是一种环境刺激,所有生物都暴露在光下。大量研究表明,细菌可以通过光感受器蛋白调节毒力因子。油菜黄单胞菌。油菜属(campestris, Xcc)是引起十字花科作物系统性血管病黑腐病的病原菌。典型症状包括叶缘发出的v型黄色病变和叶脉变黑。在之前的工作中,我们已经证明Xcc具有功能性细菌色素(XccBphP),可以调节其对红光和远红光的毒力。除了XccBphP蛋白外,Xcc基因组还编码一种蓝光光感受器,一种含光氧电压(LOV)结构域的蛋白,其输出模块为组氨酸激酶(HK)。在这里,我们展示了两种光感受器都能够感知蓝光。通过对lov基因的敲除和补充菌株进行功能损失和增益实验,我们证明了XccLOV是一个功能性光感受器。蓝光对游泳运动有负面影响,而黄原胶的产生受XccBphP的调控,且与蓝光无关。此外,我们的研究表明,蓝光改变了生物膜的结构模式,增强了毒力。总的来说,这些结果揭示了一些Xcc毒力因子是通过至少两个光感受器来调节蓝光的。
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引用次数: 0
Sunscreens in pigmentary disorders: time to revise the message. 防晒霜对色素紊乱的影响:是时候修改信息了。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-02-24 DOI: 10.1007/s43630-025-00688-w
Sahngeun Jenny Mun, Vanessa Lee, Monisha Gupta

Current sunscreen messaging centres around skin cancer prevention, with an emphasis on mitigating the damaging effects of ultraviolet B (UVB) radiation. Darker skin is believed to be better protected against UVB owing to its higher melanin content, and therefore, this messaging has been largely targeted at people with lighter skin tones. This is reflected by low sunscreen use by people of darker skin types. However, visible light (VL) is now being appreciated as a culprit behind exacerbation of disorders of hyperpigmentation such as melasma and post-inflammatory hyperpigmentation (PIH) which is known to significantly impair quality of life (QoL) of those affected. The role of VL in melanogenesis is not well known to patients nor to dermatologists and is a missed opportunity in the management of pigmentary disorders. We propose that changing the terminology from 'sunscreen' to 'light protection' acknowledges the central role of VL in melanogenesis, underlining the importance of VL protection and making the messaging more inclusive for people of all skin colours.

目前有关防晒霜的信息主要围绕预防皮肤癌展开,重点是减轻紫外线B (UVB)辐射的破坏性影响。深色皮肤被认为能更好地抵御中波紫外线,因为深色皮肤的黑色素含量更高,因此,这一信息主要针对肤色较浅的人。这反映在肤色较深的人很少使用防晒霜上。然而,可见光(VL)现在被认为是加重色素沉着障碍(如黄褐斑和炎症后色素沉着(PIH))的罪魁祸首,众所周知,这些疾病会严重损害患者的生活质量(QoL)。VL在黑色素形成中的作用对患者和皮肤科医生都不是很清楚,并且在色素紊乱的管理中错失了机会。我们建议将术语从“防晒霜”改为“光防护”,承认VL在黑色素形成中的核心作用,强调VL防护的重要性,并使信息更具包容性,适用于所有肤色的人。
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引用次数: 0
Synthesis and biological activity, photophysical, photochemical properties of tetra substituted magnesium phthalocyanine. 四取代酞菁镁的合成及其生物活性、光物理、光化学性质。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-02-15 DOI: 10.1007/s43630-025-00686-y
Sadin Özdemir, Derya Güngördü Solğun, Gülay Giray, Mehmet Salih Ağırtaş

The compound 4-(2-((1H-benzo[d]imidazol-2-yl) thio) phenoxy) phthalonitrile was obtained from the reaction of 2-nitrophenol, 4-nitrophthalonitrile and 2-mercaptobenzimidazole. This compound was reacted with magnesium Chloride (MgCl2) to yield tetrakis-[(2-((1H-benzo[d]imidazol-2-yl) thio) phenoxy) phthalocyaninato] magnesium II. New compounds were characterized by UV-vis, 1H NMR, 13C NMR, FTIR and Mass spectra. Electronic spectra aggregation study of magnesium phthalocyanine compound in various concentrations and diverse solvents was performed. Photoluminescence spectra of magnesium phthalocyanine in different solvents were investigated. The biological activities of 3 and 4 compounds were investigated. The results showed that 4 had excellent antioxidant and antidiabetic activities as 75.71% and 81.83%, respectively. 3 and 4 had deoxyribonucleic acid (DNA) cleavage ability and 4 caused a double-strand fracture in plasmid DNA at 100 and 200 mg/L. Both compounds showed antimicrobial activity and also 4 was more effective against pathogenic microorganisms than 3. Photodynamic antimicrobial therapy of test compound was also more effective than without irradiation. The highest biofilm inhibition of 3 and 4 was 78.28% and 98.49% for S. aureus and also 73.95% and 91.13% for P. aeruginosa, respectively. Finally, both compounds demonstrated %100 microbial cell viability inhibition at 100 mg/L. Overall, the study suggests that both 3 and 4 have potential for further development as therapeutic agents.

以2-硝基苯酚、4-硝基邻苯二腈和2-巯基苯并咪唑为原料,合成了化合物4-(2-((1h -苯并[d]咪唑-2-基)硫代)苯氧基)邻苯二腈。该化合物与氯化镁(MgCl2)反应制得[(2-((1h -苯并[d]咪唑-2-基)硫代)苯氧基)酞菁酸]四烷基镁II。通过紫外可见光谱、1H NMR、13C NMR、FTIR和质谱对新化合物进行了表征。对酞菁镁化合物在不同浓度和不同溶剂下的电子光谱聚集进行了研究。研究了酞菁镁在不同溶剂中的光致发光光谱。对其中3和4个化合物的生物活性进行了研究。结果表明,其中4种具有较好的抗氧化和抗糖尿病活性,分别为75.71%和81.83%。3和4具有脱氧核糖核酸(DNA)切割能力,4在100和200 mg/L时可引起质粒DNA双链断裂。两种化合物均具有抑菌活性,且4对病原菌的抑菌效果优于3。试验化合物的光动力抗菌治疗也比不照射更有效。3和4对金黄色葡萄球菌的生物膜抑制率最高,分别为78.28%和98.49%,对铜绿假单胞菌的生物膜抑制率分别为73.95%和91.13%。最后,两种化合物在100 mg/L时均表现出%100的微生物细胞活力抑制作用。总的来说,研究表明3和4都有作为治疗剂进一步开发的潜力。
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引用次数: 0
Reactions to disclosed biofeedback information on skin DNA damage in individuals after a beach holiday: a mixed methods intervention study. 海滩度假后对个人皮肤DNA损伤生物反馈信息的反应:一项混合方法干预研究。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-01-28 DOI: 10.1007/s43630-024-00677-5
Nynne Johanne Sahl Frederiksen, Ida Schwarz Thorsteinsson, Catharina Margrethe Lerche, Jonatan Riber Granborg, Merete Hædersdal, Peter Dalum, Brian Køster

Background: The incidence of skin cancer among Danes is one of the highest in the world. Most skin cancers are, however, avoidable with sun protection and reduction of exposure. One way to increase awareness could be through personal biofeedback information about skin DNA damage.

Objective: This study investigates the influence of biofeedback information about skin DNA damage on Danish beach holiday travelers' perception of risk of developing skin cancer and motivations for behaviour change.

Methods: The intervention experiment included 20 participants aged 36-56 years, travelling to destinations with a high UV-index in February/March 2023. A new technology for detecting skin DNA damage in urine was used. Each participant was required to provide urine samples before and after travelling on holiday and participate in an interview about risk perceptions. The interviews were semi-structured and included the disclosure of DNA damage obtained during the holiday. Risk perceptions were assessed using a scale before and after the disclosure of biofeedback information.

Results: We identified key elements affecting perceived susceptibility of skin cancer as well as central barriers for behaviour change. The intervention increased risk perceptions for 35% of participants, and 30% expressed intentions to adopt more sun protective practices. However, most participants' perceived susceptibility to skin cancer did not change significantly, as the DNA damage still appeared too abstract.

Conclusion: The findings suggest that biofeedback information can increase risk perceptions related to skin cancer and initiate intended behaviour change for some. Larger scale studies are needed and should include quantification of the individual DNA damage thereby making the assessed risk more relatable and personally relevant.

背景:丹麦人是世界上皮肤癌发病率最高的国家之一。然而,大多数皮肤癌是可以通过防晒和减少暴露来避免的。提高意识的一种方法是通过皮肤DNA损伤的个人生物反馈信息。目的:本研究探讨皮肤DNA损伤的生物反馈信息对丹麦海滩度假游客患皮肤癌风险认知和行为改变动机的影响。方法:干预实验包括20名年龄在36-56岁之间,于2023年2 / 3月前往高紫外线指数旅游目的地的参与者。采用了一种检测尿液中皮肤DNA损伤的新技术。每位参与者被要求在度假旅行前后提供尿液样本,并参加关于风险认知的访谈。采访是半结构化的,包括披露在假期中获得的DNA损伤。在生物反馈信息披露前后使用量表评估风险感知。结果:我们确定了影响皮肤癌易感性的关键因素,以及行为改变的主要障碍。干预增加了35%的参与者对风险的认知,30%的参与者表示愿意采取更多的防晒措施。然而,大多数参与者对皮肤癌的易感性并没有明显的变化,因为DNA损伤仍然显得过于抽象。结论:研究结果表明,生物反馈信息可以增加与皮肤癌相关的风险认知,并引发一些人的预期行为改变。需要更大规模的研究,并应包括个体DNA损伤的量化,从而使评估的风险更加相关和个人相关。
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引用次数: 0
Solvatochromism and cis-trans isomerism in azobenzene-4-sulfonyl chloride. 偶氮苯-4-磺酰氯的溶剂致变色和顺反异构。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-01-23 DOI: 10.1007/s43630-025-00684-0
İsa Sıdır, Yadigar Gülseven Sıdır, Halil Berber, Rui Fausto

Solvatochromism exhibited by azobenzene-4-sulfonyl chloride (here abbreviated as Azo-SCl) has been investigated in a series of non-polar, polar-aprotic and polar-protic solvents. The UV-vis spectra of Azo-SCl exhibit two long-wavelength bands, observed at 321-330 nm (band-I) and 435-461 nm (band-II), which are ascribed to the π*-π (S2 ← S0) and π*-n (S1 ← S0) transitions, respectively. The shorter wavelength band indicates a reversal in solvatochromism, from negative to positive solvatochromism, for a solvent with a dielectric constant of 32.66 (which is characteristic of methanol), while the longer wavelength band signposts negative solvatochromism in all range of solvent's dielectric constant investigated, demonstrating different interactions with the solvents in the S2 and S1 excited states. Using Catalán and Kamlet-Taft solvation energy models, we found that the shift in the solvatochromic behavior of band-I (S2 ← S0) happens because solvent dipolarity/polarizability and hydrogen bonding affect the S2 state in opposite ways. Dipolarity/polarizability stabilizes the S2 state compared to the ground state, while hydrogen bonding destabilizes it. In contrast, for S1, both effects work together to destabilize the excited state. For all studied solvents, UV irradiation (λ ≥ 311 nm; room temperature) was found to lead to fast trans-cis azo photoisomerization. In the absence of light, the photogenerated cis form quickly converts back to the trans form. Interpretation of the experimental data is supported by quantum chemical calculations undertaken within the Density Functional Theory (DFT) framework, including Time Dependent DFT calculations for excited states.

本文研究了偶氮苯-4-磺酰氯(简称Azo-SCl)在非极性、极性-非质子和极性-质子溶剂中的溶剂致变色现象。偶氮- scl的紫外可见光谱呈现出321 ~ 330 nm(波段i)和435 ~ 461 nm(波段ii)两个长波段,分别属于π*-π (S2←S0)和π*-n (S1←S0)跃迁。对于介电常数为32.66(甲醇的特征)的溶剂,较短的波长波段表示溶剂变色从负向正的逆转,而较长的波长波段表示溶剂在所有介电常数范围内的负溶剂变色,表明在S2和S1激发态下与溶剂的不同相互作用。利用Catalán和Kamlet-Taft溶剂化能模型,我们发现,由于溶剂的双极性/极化性和氢键以相反的方式影响S2态,导致了带i (S2←S0)溶剂化变色行为的转变。与基态相比,双极性/极化性使S2态稳定,而氢键使其不稳定。相反,对于S1,两种效应共同作用使激发态不稳定。对于所有研究溶剂,紫外辐照(λ≥311 nm;室温)导致快速的反式顺式偶氮光异构化。在没有光的情况下,光生成的顺式迅速转化回变换式。实验数据的解释由密度泛函理论(DFT)框架内进行的量子化学计算支持,包括激发态的时间相关DFT计算。
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引用次数: 0
β-Nicotinamide mononucleotide blocks UVB-induced collagen reduction via regulation of ROS/MAPK/AP-1 and stimulation of mitochondrial proline biosynthesis. β-烟酰胺单核苷酸通过调控ROS/MAPK/AP-1和刺激线粒体脯氨酸生物合成来阻断uvb诱导的胶原还原。
IF 2.7 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-02-01 Epub Date: 2025-03-01 DOI: 10.1007/s43630-025-00692-0
Yue Zhang, Chen Ai, Fangzhou Huang, Ji-Li Zhao, Yixin Ling, Weijing Chen, Zhenzhu Li, Yu Wang, Fei Gao, Siqi Li, Wei Gao, Yu-Shuai Wang

β-Nicotinamide mononucleotide (NMN), as a precursor of long-lived protein co-factor nicotinamide adenine dinucleotide (NAD+) in the human body, has demonstrated promising clinical value in treating photoaging and skin wounds. Previous research showed that NMN possessed significant skin protection against UVB-induced photoaging and promoted collagen synthesis. However, its potential mechanism remains unclear. This study aimed to investigate whether NMN improved UVB-induced collagen degradation by regulating ROS/MAPK/AP-1 signaling and stimulating mitochondrial proline biosynthesis. The results showed that NMN notably inhibited UVB-induced ROS production and down-regulated the MAPK/AP-1 signaling pathway. In addition, NMN significantly increased proline levels in mitochondria, which acted as the primary raw materials for collagen synthesis. Further mechanistic analysis revealed that NMN increased the levels of mitochondrial NAD+ and NADP(H). Besides, NMN supplementation activated pyrroline-5-carboxylatesynthetase (P5CS), a key enzyme in proline biosynthesis, by increasing SIRT3 levels. However, the promoting effects of NMN on proline and collagen synthesis were significantly inhibited when 3-TYP, a SIRT3 inhibitor, was combined applied. Meanwhile, the effects of NMN on collagen synthesis were reversed when the solute carrier family 25 member 51, a mammalian mitochondrial NAD+ transporter, was knocked down. Moreover, animal experiments indicated that NMN ameliorated UVB-induced collagen fiber degradation by activating the SIRT3/P5CS signaling. These results revealed that NMN could combat UVB-induced collagen depletion by regulating the ROS/MAPK/AP-1 and proline synthesis.

β-烟酰胺单核苷酸(nicotinamide mononucleotide, NMN)作为人体内长寿命蛋白辅助因子nicotinamide adenine dinucleotide (NAD+)的前体,在治疗光老化和皮肤损伤方面具有良好的临床应用价值。先前的研究表明,NMN对uvb诱导的光老化具有显著的皮肤保护作用,并促进胶原合成。然而,其潜在机制尚不清楚。本研究旨在探讨NMN是否通过调节ROS/MAPK/AP-1信号和刺激线粒体脯氨酸生物合成来改善uvb诱导的胶原降解。结果表明,NMN显著抑制uvb诱导的ROS生成,下调MAPK/AP-1信号通路。此外,NMN显著提高了线粒体中的脯氨酸水平,而脯氨酸是胶原合成的主要原料。进一步的机制分析显示,NMN增加了线粒体NAD+和NADP(H)的水平。此外,添加NMN可通过提高SIRT3水平激活脯氨酸生物合成的关键酶pyroline -5-carboxylatesynthetase (P5CS)。而与SIRT3抑制剂3-TYP联合使用时,NMN对脯氨酸和胶原合成的促进作用被显著抑制。同时,当哺乳动物线粒体NAD+转运蛋白溶质载体家族25成员51被敲除时,NMN对胶原合成的影响被逆转。此外,动物实验表明,NMN通过激活SIRT3/P5CS信号通路,改善了uvb诱导的胶原纤维降解。这些结果表明,NMN可以通过调节ROS/MAPK/AP-1和脯氨酸合成来对抗uvb诱导的胶原耗损。
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引用次数: 0
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Photochemical & Photobiological Sciences
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