Anthracene-Fused Oligo-BODIPYs: A New Class of π-Extended NIR-Absorbing Materials

Large π-conjugated systems are key in the area of molecular materials. Herein, we prepare via Au^I-catalyzed cyclization a series of fully π-conjugated anthracene-fused oligo-BODIPYs. Their structural and optoelectronic properties were studied by several techniques, ranging from X-ray, UV/Vis, and cyclic voltammetry to transient absorption spectroscopy. As a complement, their electronic structures were explored by means of Density Functional Theory (DFT) calculations. Depending on the size and shape of the π-conjugated skeleton, unique features—such as face-to-face supramolecular organization, NIR absorption and fluorescence as well as strong electron accepting character—were noted. All in all, the aforementioned features render them valuable for technological applications.     

Strong Electronic Communication in Linearly Elongated Rylenes Featuring Tunable Bridges

A modified synthetic pathway towards perylene-perylene dimers and a facile purification method to obtain the regioisomerically pure syn- and anti-isomers are reported. In addition, a novel perylene-naphthalene heterodimer with 30 conjugated π-electron pairs was designed and synthesized on the basis of a previously described precursor and the resulting regioisomers were separated from each other. Thereby, the opto-electronic properties of the linearly elongated chromophores could be investigated regarding the differences in length of their aromatic system and the configuration of the isomers. Further tuning of their energy gaps was realized via protonation and methylation of the dibenzimidazole-bridging unit. Extraordinary red-shifts of the absorption maxima of 62 nm for the methylated and 92 nm for the protonated perylene-perylene anti-isomer could be achieved. Moreover, the maxima for the syn-isomer could be shifted bathochromically by 87 and 113 nm, respectively.     

Advanced combined application of μ-X-ray diffraction/μ-X-ray fluorescence with conventional techniques for the identification of pictorial materials from Baroque Andalusia paintings

The process of investigating paintings includes the identification of materials to solve technical and historical art questions, to aid in the deduction of the original appearance, and in the establishment of the chemical and physical conditions for adequate restoration and conservation. In particular, we have focused on the identification of several samples taken from six famous canvases painted by Pedro Atanasio Bocanegra, who created a very special collection depicting the life of San Ignacio, which is located in the church of San Justo y Pastor of Granada, Spain. The characterization of the inorganic and organic compounds of the textiles, preparation layers, and pictorial layers have been carried out using an XRD diffractometer, SEM observations, EDX spectrometry, FT-IR spectrometry (both in reflection and transmission mode), pyrolysis/gas chromatography/mass spectrometry and synchrotron-based μ-X-ray techniques. In this work, the advantages over conventional X-ray diffraction of using combined synchrotron-based μ-X-ray diffraction and μ-X-ray fluorescence in the identification of multi-layer paintings is demonstrated.     

Determination of traces of polychlorinated biphenyls in pigments

PCB patterns in a new pigment brand are characterized using GC-MS in the single ion monitoring (SIM) mode. Specific PCBs are then used as external standards for GC-ECD quantification. The following PCB isomers or groups of isomers have to be determined (CB = chlorobiphenyl): total diCBs, 3,3′ diCB, 2,4,5-triCB, 2,2′,4,4′-tetraCB, 2,2′,5,5′-tetraCB, total pentaCB, total hexaCB. Capillary gas chromatography is performed on preseparated solutions (LC) of pigment. An electron caputure detector (ECD) is used for PCB detection and quantification. Calibration is based on the peak areas of external standards and the PCB isomers in the samples, all normalized for internal standard peak areas. Total concentrations of diCB, hexaCB, or pentaCB in a sample are calculated by summing the individual PCB isomer concentrations within the correcsponding elution ranges. Determination limits lie in the range of 1 mg/PCB-isomer/kg pigment.     

广元千佛崖石窟石刻彩妆颜料的分析

四川省广元千佛崖石窟是四川境内最大的石窟寺和摩崖造像群,承载着古代社会的历史信息,对研究当时的政治、文化和社会生活意义重大。千佛崖石窟在自然环境因素的长期作用下,目前受到多种严重病害的侵蚀,亟待保护。为了获取石刻彩妆的成分与工艺信息以支撑彩妆的保护工作,应用X射线衍射分析、剖面显微分析、扫描电镜能谱分析、激光拉曼光谱分析等方法,对广元千佛崖8处洞窟的已脱落彩妆颜料层样品进行了分析。X射线衍射分析鉴定出了铁红(Fe₂O₃)、朱砂 (HgS)、铅丹(Pb₃O₄)、炭黑等颜料成分,以及铅白 (PbSO₄)、石膏(CaSO₄·2H₂O)、长石、二氧化硅等打底层和岩体的组分,验证了样品脱落的原因是岩体的劣化。剖面显微分析和扫描电镜能谱分析表明,不同洞窟的彩妆制作工艺有区别,有的颜料直接施加在岩体表面,有的则在颜料层和岩体间有一层主要为硫酸铅的打底层;样品表面蓝绿色颜料的含量很少,仅通过激光共聚焦显微拉曼光谱成功地识别出来,其鉴定结果为蓝铜矾[Cu₄SO₄(OH)₆·2H₂O]。蓝铜矾作为颜料使用的报道很少。由于其矿物含量较少但分布广泛,古代一般不将其分离出来单独使用,而人工合成的碱式硫酸铜类颜料布勒门绿（Bremen green）出现于18世纪-19世纪,如果有纯碱式硫酸铜单独使用的情况出现,就意味着有近现代重绘的可能性,将有助于彩绘类文物保存历史的判断。该研究不仅为千佛崖石刻彩妆的保护提供了依据,丰富了文化遗产中使用蓝铜矾颜料的案例,更对彩妆的保存历史研究有潜在价值。     

Near-crater discoloration of white lead in wall paintings during laser induced breakdown spectroscopy analysis

During Laser-Induced Breakdown Spectroscopy (LIBS) analysis of white lead pigment (basic lead carbonate, 2PbCO₃·Pb(OH)₂), used in wall paintings of historical interest, a yellow–brown discoloration has been observed around the crater. This phenomenon faded after a few days exposure under ambient atmosphere. It was established that the mechanism of this discoloration consists in lead oxides (PbO) formation. It was verified by further experiments under argon atmosphere that recombination of lead with oxygen in the plasma plume produces the oxides, which settle around the crater and induce this discoloration. The impact of discoloration on the artwork's aesthetic aspect and the role of atmosphere on discoloration attenuation are discussed. The mechanism is studied on three other pigments (malachite, Prussian blue and ultramarine blue) and threshold for discoloration occurrence is estimated.     

Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C—H bond activation

BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. An overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C-H functionalization of the BODIPY framework have been provided.     

Analytical contributions to the evaluation of painting authenticity from Princely church of Curtea de Arges

The present study contains the analyses performed for pigment samples taken from the Princely church of Curtea de Arges, one of the oldest churches in Romania. The results of our investigations have shown the source of these samples, thus being identified the pigments: natural ultramarine, cinnabar, red earth, and calcium carbonate in the painting from the 14th century, the pigments: lead white, zinc white, and Prussian blue in the repainting from the 19th century and the pigments zinc white, titanium dioxide white, bone white, yellow ochre, red ochre, green earth, artificial ultramarine, and mars red in the interventions carried out in the 20th century. The analyses consisted of light microscopy (LM) and microchemical tests, as well as energy dispersive X-ray (EDX) analysis. This system of analyses allows one to precisely determine the authenticity of certain pigments, thus avoiding the dating errors for different interventions carried out on the original mural painting from the Saint Nicholas Princely church of Curtea de Arges.     

The Search for Highly Colored Organic Compounds

Until now the study of organic compounds in which the π-electron system is excited by absorbed light has been mainly concentrated on the ultraviolet and visible regions of the electromagnetic spectrum. Various new applications, such as the use of conjugated organic compounds as dye lasers or as materitals for storing information with the help of diode lasers, led to the synthesis of new compounds which absorb light in the near in infrared (NIR). It is possible to use structure-color relationships to predict the properties of such new compounds when they belong to dyestuff classes which have already been studied in detail; in this case the approach involves decreasing the energy difference between the ground state and the first excited state. A less conventional starting point is provided by molecular structures in which from the outset there is only a very small energy difference between the lowest-energy electronic states; such diradicaloid molecules occupy a special position among the various types of organic compounds. It is possible by means of suitable structural modification to stabilize such molecules in a singlet from which absorbs light at very long wavelengths (i.e. at small wave numbers).