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Synthesis and Characterization of Multifunctional Symmetrical Squaraine Dyes for Molecular Photovoltaics by Terminal Alkyl Chain Modifications 通过末端烷基链修饰合成和表征用于分子光伏技术的多功能对称水杨酸染料
Pub Date : 2024-07-16 DOI: 10.3390/colorants3030014
Kota Mori, Y. Kurokawa, Shyam S. Pandey
Novel far-red sensitive symmetric squaraine (SQ) dyes with terminal alkyl chain modifications were designed, synthesized, and characterized, aiming towards imparting multifunctionalities such as photosensitization, dye aggregation prevention, and source of electrolyte components. The dye sensitizer SQ-80 with alkyl chain terminal modifications consisting of 1-methylimidazolium iodide was designed and synthesized as a new dye sensitizer for DSSCs based on symmetric SQ-4 without any terminal modification used as reference. Upon adsorption on the mesoporous TiO2 surface, SQ-80 demonstrated reduced dye aggregation and stronger binding to the TiO2 surface, leading to enhanced durability of DSSCs. Apart from the most common photosensitization behavior, the newly designed dye demonstrated multifunctionalities such as aggregation prevention and electrolyte functionality, utilizing iodine-based redox electrolytes in the presence and absence of I2 and LiI additives. In the absence of LiI and I2, a mixture of SQ-77 with alkyl chain terminal modifications consisting of iodide and SQ-80 demonstrated a photoconversion efficiency of 1.54% under simulated solar irradiation, which was about six times higher compared with the reference dye SQ-4 (0.24%) (having no alkyl chain terminal modification).
我们设计、合成并表征了具有烷基链末端修饰的新型远红敏感对称鳞红素(SQ)染料,旨在赋予其光敏化、防止染料聚集和电解质成分来源等多功能性。设计并合成了由 1-甲基碘化咪唑鎓组成的烷基链末端修饰的染料敏化剂 SQ-80,它是一种用于 DSSC 的新型染料敏化剂,以未进行任何末端修饰的对称 SQ-4 为参考。SQ-80 吸附在介孔二氧化钛表面后,染料聚集现象减少,与二氧化钛表面的结合力增强,从而提高了 DSSC 的耐用性。除了最常见的光敏行为外,新设计的染料还具有多功能性,如在有和没有 I2 和 LiI 添加剂的情况下,利用碘基氧化还原电解质防止聚集和电解质功能。在没有 LiI 和 I2 的情况下,碘化烷基链端修饰的 SQ-77 与 SQ-80 的混合物在模拟太阳辐照下的光电转换效率为 1.54%,与参考染料 SQ-4(0.24%)(无烷基链端修饰)相比高出约六倍。
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引用次数: 0
Exploring the Role and Variability of 3d Transition Metal Complexes in Artistic Coloration through a Bottom-Up Scientific Approach 通过自下而上的科学方法探索 3d 过渡金属配合物在艺术色彩中的作用和可变性
Pub Date : 2024-06-13 DOI: 10.3390/colorants3020012
Alexandra Coia, Jackson Ruddick, Olivia Kuang, Li-Qiong Wang
Transition metal complexes have historically played a pivotal role in creating vibrant pigments utilized across artistic mediums such as ceramics, paintings, and glass mosaics. Despite their extensive historical use, our understanding of the mechanisms governing transition metal complex behavior has predominantly emerged in recent times, leaving numerous aspects of this process ripe for exploration. These complexes exhibit striking color variations under diverse conditions when employed in pigment formulations. This review utilizes a bottom-up scientific approach, spanning from microscopic to macroscopic scales, to unravel the molecular origins of the colors generated by transition metal complexes in pigments and ceramic glazes. Advanced spectroscopy techniques and computational chemistry play pivotal roles in this endeavor, highlighting the significance of understanding and utilizing analytical data effectively, with careful consideration of each technique’s specific application. Furthermore, this review investigates the influence of processing conditions on color variations, providing valuable insights for artists and manufacturers aiming to enhance the precision and quality of their creations while mitigating environmental impact.
历史上,过渡金属络合物在陶瓷、绘画和玻璃马赛克等艺术媒介中使用的鲜艳颜料的制作过程中发挥了举足轻重的作用。尽管过渡金属复合物在历史上被广泛使用,但我们对过渡金属复合物行为机理的了解主要是在近代才出现的,因此对这一过程的许多方面进行探索的时机已经成熟。在颜料配方中使用这些复合物时,它们在不同条件下会表现出惊人的色彩变化。本综述采用自下而上的科学方法,从微观到宏观,揭示颜料和陶瓷釉料中过渡金属复合物产生色彩的分子起源。先进的光谱学技术和计算化学在这一研究中发挥了关键作用,凸显了有效理解和利用分析数据的重要性,同时也仔细考虑了每种技术的具体应用。此外,本综述还研究了加工条件对颜色变化的影响,为艺术家和制造商提供了有价值的见解,这些艺术家和制造商旨在提高其作品的精度和质量,同时减轻对环境的影响。
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引用次数: 0
Synthesis of Green Brucite [NixMg1−x(OH)2] by Incorporation of Nickel Ions in the Periclase Phase (MgO) Applied as Pigments 通过在用作颜料的包晶相(氧化镁)中掺入镍离子合成绿色青金石 [NixMg1-x(OH)2]
Pub Date : 2024-05-20 DOI: 10.3390/colorants3020011
C. Siqueira, Aline B Schons, Patricia Appelt, Weslei D. Silva, Nayara Balaba, Mário A. A. Cunha, F. Anaissi
Magnesium oxide is typically white and can be colorized with transition metal insertion by doping. We present the preparation of a green-colored hydroxide by the exchange of Mg2+ on the crystalline lattice with Ni2+ in MgO, using three nickel salts. MgOst was prepared by the colloidal starch suspension method, using cassava starch. The oxides and hydroxides, before and after, were characterized by X-ray diffraction (XRD), and show that a phase change occurs: a transition from periclase (MgO) to brucite (Mg(OH)2) due to the incorporation of nickel ions from different salts (acetate, chloride, and nitrate), resulting in the solid solution [NixMg1−x(OH)2]. The FTIR spectrum corroborates the crystallographic structure identified through XRD patterns, confirming the formation of a crystal structure resembling brucite. The new samples present a green color, indicative of the incorporation of the Ni2+ ions. The antimicrobial activity of products resulting from the doping of magnesium oxide with nickel and the precursor MgOst was assessed through the minimum inhibitory concentration (MIC) test. The evaluation included three bacterial strains: Staphylococcus aureus (ATCC 25923), Escherichia coli (ATCC 25922), Salmonella gallinarum (ATCC 9184), and a yeast strain, Candida albicans (ATCC 10231). The obtained results were promising; the tested samples exhibited antimicrobial activity, with a MIC ranging from 0.312 to 0.625 μg.μL−1. The nickel compound, derived from the precursor chloride salt, demonstrated superior MIC activity. Notably, all tested samples displayed bactericidal activity against the S. aureus strain and exhibited a broad spectrum of inhibition, encompassing both Gram-positive and Gram-negative strains. Only the nickel compounds derived from precursors with acetate and nitrate anions demonstrated antimicrobial activity against C. albicans, exhibiting a fungistatic behavior. Based on the conducted studies, [NixMg1−x(OH)2] has emerged as a promising antimicrobial agent, suitable for applications requiring the delay or inhibition of bacterial growth.
氧化镁通常是白色的,通过掺杂过渡金属可使其着色。我们利用三种镍盐,通过氧化镁中的镍2+与晶格上的Mg2+交换,制备了一种绿色氢氧化物。MgOst 是用木薯淀粉通过胶体淀粉悬浮法制备的。X 射线衍射 (XRD) 对制备前后的氧化物和氢氧化物进行了表征,结果表明发生了相变:由于不同盐类(醋酸盐、氯化物和硝酸盐)中的镍离子的加入,发生了从橄榄石(MgO)到青金石(Mg(OH)2)的转变,形成了固溶体 [NixMg1-x(OH)2]。傅立叶变换红外光谱证实了通过 X 射线衍射图谱确定的晶体结构,确认形成了类似于青金石的晶体结构。新样品呈现绿色,表明其中含有 Ni2+ 离子。通过最小抑菌浓度(MIC)测试评估了掺入镍的氧化镁和前体 MgOst 所产生的产品的抗菌活性。评估包括三种细菌菌株:金黄色葡萄球菌(ATCC 25923)、大肠杆菌(ATCC 25922)、胆沙门氏菌(ATCC 9184)和一种酵母菌株白色念珠菌(ATCC 10231)。测试结果表明,测试样品具有抗菌活性,其 MIC 值为 0.312 至 0.625 μg.μL-1。从前体氯盐中提取的镍化合物显示出更高的 MIC 活性。值得注意的是,所有测试样品都对金黄色葡萄球菌菌株具有杀菌活性,并表现出广泛的抑菌谱,包括革兰氏阳性和革兰氏阴性菌株。只有从带有醋酸阴离子和硝酸阴离子的前体中提取的镍化合物才对白僵菌具有抗菌活性,表现出抑菌作用。根据所进行的研究,[NixMg1-x(OH)2] 已成为一种很有前途的抗菌剂,适用于需要延缓或抑制细菌生长的应用领域。
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引用次数: 0
Colorants: Moving to the Next Stage 着色剂:迈向下一阶段
Pub Date : 2024-05-14 DOI: 10.3390/colorants3020010
Anthony Harriman
As Editor-in-Chief of Colorants [ISSN: 2079-6447], I have watched the progressive growth of this journal and witnessed the expansion of topics way beyond the initial consideration [...]
作为《着色剂》[ISSN: 2079-6447]的主编,我见证了该期刊的逐步发展,并目睹了其主题的扩展远远超出了最初的考虑范围 [...] 。
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引用次数: 0
Highly Stable Hybrid Pigments Prepared from Organic Chromophores and Fluorinated Hydrotalcites 用有机发色团和含氟氢铝酸盐制备高稳定性杂化颜料
Pub Date : 2024-05-09 DOI: 10.3390/colorants3020009
Magali Hernández, Carlos Felipe, Ariel Guzmán-Vargas, José Luis Rivera, Enrique Lima
Structural hydroxide groups in layered magnesium–aluminum double hydroxides were partially replaced by fluoride ions. Fluorinated and fluorine-free materials were used as hosts for two dyes, carminic acid and hydroxyl naphthol blue, resulting in a hybrid pigment color palette. The pigments were produced by two ways, either incorporating chromophore during the synthesis of the layered double hydroxide or in a post-synthesis step through the memory effect of the LDHs. Additionally, the pigments were protected with a magnesium hydroxide phase to prevent the color from fading over time. The pigments were stable for periods as long as 10 years. The color properties of the pigments were significantly influenced by the host of dye since the presence of fluorine directly influences the acid–base properties of the layered double hydroxides. The pigments conferred their color to white cream in the preparation of colored creams. The colored creams acquired the color of the layered pigment.
层状镁铝双氢氧化物中的氢氧基结构被氟离子部分取代。含氟和不含氟的材料被用作两种染料--胭脂虫酸和羟基萘酚蓝--的宿主,从而产生了混合颜料色谱。生产颜料的方法有两种,一种是在合成层状双氢氧化物时加入发色团,另一种是在合成后通过层状双氢氧化物的记忆效应加入发色团。此外,颜料还受到氢氧化镁相的保护,以防止颜色随着时间的推移而褪色。这些颜料的稳定性可达 10 年之久。由于氟的存在会直接影响层状双氢氧化物的酸碱特性,因此颜料的颜色特性受到染料主体的显著影响。在制备有色膏霜时,这些颜料会赋予白膏霜颜色。有色膏体获得了层状颜料的颜色。
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引用次数: 0
Solid-State Luminescence with a Large Stokes Shift in Starch Functionalized with Low-Content ESIPT Dye 低含量 ESIPT 染料官能化淀粉的固态发光与大斯托克斯偏移
Pub Date : 2024-04-03 DOI: 10.3390/colorants3020007
Emerson Colonetti, L. C. da Luz, F. Rodembusch
Herein, we present the preparation of solid-state photoactive starches with a large Stokes shift, along with the resulting materials. In this investigation, 2-(2′-hydroxyphenyl)benzazole derivatives responsive to intramolecular proton transfer in the excited state (ESIPT) were covalently bonded to the polymeric structure of starch through a reaction involving an isothiocyanate group and the hydroxyl groups of starch. These compounds exhibit absorption at approximately 350 nm, which is related to fully spin- and symmetry-allowed π → π* electronic transitions, and solid-state fluorescence at approximately 500 nm, which features a significant separation between the absorption and emission maxima (~9000 cm−1). Due to the minimal use of fluorophores in functionalized starch preparation, this modification does not affect the original properties of the starch. Finally, photoactive starch-based films with significantly high transparency were successfully produced.
在此,我们介绍了具有较大斯托克斯位移的固态光活性淀粉的制备方法以及所得到的材料。在这项研究中,通过异硫氰酸酯基团与淀粉羟基的反应,将对激发态分子内质子转移(ESIPT)有反应的 2-(2′-羟基苯基)苯甲唑衍生物共价键合到淀粉的聚合物结构上。这些化合物在大约 350 纳米波长处显示出吸收,这与完全自旋和对称允许的 π → π* 电子跃迁有关;在大约 500 纳米波长处显示出固态荧光,其特点是吸收和发射最大值之间有明显的分离(大约 9000 厘米-1)。由于在制备功能化淀粉时只使用了极少量的荧光团,因此这种改性不会影响淀粉的原有特性。最后,成功制备出了透明度极高的光活性淀粉基薄膜。
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引用次数: 0
Optical Investigation of 2-amino-7-isocyanofluorene, a Novel Blue-Emitting Solvatochromic Dye 2-amino-7-isocyanofluorene -- 一种新型蓝色发光溶色染料的光学研究
Pub Date : 2024-03-25 DOI: 10.3390/colorants3020006
Bence Kontra, Zoltán Mucsi, L. Vanyorek, Miklós Nagy
Smart solvatochromic isocyano-aminoarenes (ICAArs) have been gaining attention owing to their unique photophysical, antifungal and anticancer properties. Using a simple dehydration reaction with in situ-generated dichlorocarbene, we prepared 2-amino-7-isocyanofluorene (2,7-ICAF). We studied the effect of the longer polarization axis provided by the fluorene core on the spectral properties and we also compared it to those of the starting diamine. 2,7-ICAF shows a clear solvatochromic behavior close to the blue part (370–420 nm) of the visible spectrum. Quantum chemical calculations show internal charge transfer (ICT) between the donor amino and the electron-withdrawing isocyano groups. 2,7-ICAF has high molar absorptivity (ε = 15–18·103 M−1cm−1) and excellent quantum yield (Φf = 70–95%) in most solvents; however, its fluorescence is completely quenched in water. The high brightness (ε·Φf) and close to zero quantum yield in water may be favorable in biolabeling applications, where background fluorescence should be kept minimal. Overall, 2,7-ICAF shows enhanced photophysical properties compared to its previously investigated relative 4-amino-4′-isocyano-1,1′-biphenyl (4,4′-ICAB).
智能溶解变色异氰酸芴(ICAArs)因其独特的光物理、抗真菌和抗癌特性而备受关注。通过与原位生成的二氯甲烷进行简单的脱水反应,我们制备出了 2-氨基-7-异氰基芴(2,7-ICAF)。我们研究了芴核提供的较长偏振轴对光谱特性的影响,并将其与起始二胺的光谱特性进行了比较。2,7-ICAF 在靠近可见光谱的蓝色部分(370-420 纳米)显示出明显的溶解变色特性。量子化学计算显示,供体氨基和抽电子异氰基之间存在内部电荷转移(ICT)。2,7-ICAF 在大多数溶剂中都具有很高的摩尔吸收率(ε = 15-18-103 M-1cm-1)和出色的量子产率(Φf = 70-95%),但其荧光在水中会被完全猝灭。在水中的高亮度(ε-Φf)和接近零的量子产率可能有利于生物标记的应用,因为在这种应用中背景荧光应保持在最低水平。总体而言,2,7-ICAF 与之前研究过的 4-氨基-4′-异氰基-1,1′-联苯(4,4′-ICAB)相比,显示出更强的光物理特性。
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引用次数: 0
Azobenzene-Containing Schiff-Bases—Syntheses and Dyes Applications 含偶氮苯的席夫碱-合成与染料应用
Pub Date : 2024-02-09 DOI: 10.3390/colorants3010004
E. Léonard, China Takeda, T. Akitsu
Azo-Schiff bases contain an azo photochrome showing isomerization accompanying with color change, and an imine moiety (which can contribute to the metal complexation capability). The syntheses of these molecules will be described, and their dyes applications will be discussed, such as for fuel cells, as photometric or colorimetric sensors. In addition, liquid crystals and their antibacterial efficiencies will also be discussed.
偶氮-希夫碱含有一种偶氮光色素,会随着颜色的变化而发生异构化,还含有一个亚胺分子(可增强金属络合能力)。我们将介绍这些分子的合成方法,并讨论它们在染料方面的应用,如燃料电池、光度或色度传感器等。此外,还将讨论液晶及其抗菌效率。
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引用次数: 0
Azobenzene-Containing Schiff-Bases—Syntheses and Dyes Applications 含偶氮苯的席夫碱-合成与染料应用
Pub Date : 2024-02-09 DOI: 10.3390/colorants3010004
E. Léonard, China Takeda, T. Akitsu
Azo-Schiff bases contain an azo photochrome showing isomerization accompanying with color change, and an imine moiety (which can contribute to the metal complexation capability). The syntheses of these molecules will be described, and their dyes applications will be discussed, such as for fuel cells, as photometric or colorimetric sensors. In addition, liquid crystals and their antibacterial efficiencies will also be discussed.
偶氮-希夫碱含有一种偶氮光色素,会随着颜色的变化而发生异构化,还含有一个亚胺分子(可增强金属络合能力)。我们将介绍这些分子的合成方法,并讨论它们在染料方面的应用,如燃料电池、光度或色度传感器等。此外,还将讨论液晶及其抗菌效率。
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引用次数: 0
Development of a Carotenoid-Rich Microalgae Colorant by Microencapsulation 通过微胶囊技术开发富含类胡萝卜素的微藻着色剂
Pub Date : 2024-01-12 DOI: 10.3390/colorants3010003
Ana N. Nunes, Joana Monte, S. Rodríguez-Rojo, Isabel D. Nogueira, Luís F. Gouveia, C. Brazinha, Ana A. Matias
Dunaliella salina has been recognized as an excellent biomass source of carotenoid, which can be used as a natural orange coloring agent for food products. The most eco-friendly approach for extracting carotenoid is through supercritical carbon dioxide extraction, as it yields highly concentrated extracts while preventing pigment thermal degradation. However, there are limitations when a lipophilic extract is considered a food ingredient, in particular very difficult handling and low solubility in water-based products. The aim of this study was to develop a hydrosoluble form of a natural carotenoid-rich extract recovered from algae biomass within a biorefinery concept to be incorporated in aqueous-based food products. A two-step process was developed, starting with the emulsification of the supercritical extract into a mixture of maltodextrin and gum arabic, using soy lecithin as an emulsifier. The emulsification was followed by a spray-drying step. The impact of process variables on the encapsulation yield, efficiency, emulsion properties, and particle characteristics was studied. The resulting particles exhibited an intense orange color and good water dispersibility, facilitating uniform yellow coloring when incorporated into an aqueous-based product. Overall, spray-drying emulsions containing carotenoids derived from Dunaliella salina prove to be a promising strategy for the global market demand for natural colorants.
盐生杜莎藻(Dunaliella salina)被认为是类胡萝卜素的极佳生物质来源,可用作食品的天然橙色着色剂。提取类胡萝卜素最环保的方法是超临界二氧化碳萃取,因为这种方法既能获得高浓度提取物,又能防止色素热降解。然而,当亲脂性提取物被视为食品配料时,就会受到一些限制,特别是在水基产品中很难处理和溶解度低。本研究的目的是在生物精炼概念中开发一种水溶性的富含类胡萝卜素的天然提取物,这种提取物是从海藻生物质中提取的,可用于水基食品中。该研究开发了一种两步法,首先使用大豆卵磷脂作为乳化剂,将超临界提取物乳化成麦芽糊精和阿拉伯树胶的混合物。乳化之后是喷雾干燥步骤。研究了工艺变量对封装产量、效率、乳化特性和颗粒特征的影响。所得颗粒呈现出浓烈的橙色,并具有良好的水分散性,在加入水基产品中时可促进均匀的黄色着色。总之,含有从杜纳利藻中提取的类胡萝卜素的喷雾干燥乳剂被证明是满足全球市场对天然着色剂需求的一种有前途的策略。
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引用次数: 0
期刊
Colorants
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