Raman and infrared studies of synthetic Maya pigments as a function of heating time and dye concentration

Maya Blue is a famous indigo‐based pigment produced by the ancient Mayas. The organic/inorganic complexes inspired by Maya Blue have led to a new class of surface compounds that have novel applications to pigment industries. Materials analyzed in the present work are made by a synthetic route, and demonstrate chemical stability similar to that of the ancient Maya Blue samples. However, we have learned that stable complexes can be synthesized at much higher dye concentrations than used by the Mayas. Analysis by FT‐Raman and FT‐IR spectroscopy demonstrates the partial elimination of the selection rules for the centrosymmetric indigo, indicating distortion of the molecule. This distortion accounts for the observed color changes, as the molecular orbital structure is modified, allowing the complex to stabilize. The spectroscopic data also shows the disappearance of the indigo N H bonding, as the organic molecules incorporate into palygorskite material. A structural change of indigo to dehydroindigo during heating is suggested by this result. Infrared data confirm the loss of zeolitic water and a partial removal of structural water after the heating process. Evidence of bonding between cationic aluminum and dehydroindigo through oxygen and nitrogen is revealed by FT‐Raman measurements at higher dye concentrations. Copyright © 2007 John Wiley & Sons, Ltd.     

Characterization of indigo carmine with surface‐enhanced resonance Raman spectroscopy (SERRS) using silver colloids and island films,and theoretical calculations

The application of resonance Raman (RR) and surface‐enhanced resonance Raman (SERR) spectroscopies to the qualitative and semiquantitative analysis of the artificial dye indigo carmine has been examined using sodium‐citrate‐reduced silver colloid and island films with various roughnesses. Additional, the Raman spectrum of the solid state and density functional theory (DFT) calculations helped to a better understanding of the fully optimized geometry and of the vibrational wavenumbers of the dye. A strong chemical interaction of indigo carmine with the silver colloidal particles was observed mainly at very low concentration of 0.03 × 10⁻⁹ M and with silver film surfaces at a concentration of 10⁻⁴ M . The indigo carmine orientation possibilities while going to different metallic substrates are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Pre-columbian nanotechnology: reconciling the mysteries of the maya blue pigment

The ancient Maya combined skills in organic chemistry and mineralogy to create an important technology – the first permanent organic pigment. The unique color and stability of Maya Blue can be explained by a new model where indigo dye fills the grooves present at the surface of palygorskite clay, forming a hydrogen bonded organic/inorganic complex. Existing theory assumes the dye is dispersed inside the channels of an opaque mineral. Based on data from thermal analysis, synchrotron and neutron diffraction, ESEM and chemical modelling calculations, our new concept of Maya Blue structure resolves this contradiction and suggests some novel possibilities for more durable, environmentally benign pigments. PACS 61.66-f; 62.23.St; 61.66.Fn; 61.66.Hq     

FT‐Raman spectroscopy—a rapid and reliable quantification protocol for the determination of natural indigo dye in Polygonum tinctorium

In the recent years, Raman and IR spectroscopies have attracted increasing attention as fast, non‐invasive and widely applicable alternative analytical approaches for a variety of materials. Vibrational spectroscopy has been used in the analysis of herbal products, dyes and sensitive art objects, besides complex and aqueous biomaterials such as biopolymers or mammalian tissue. Compared to conventional analytical methods based on high‐performance liquid chromatography (HPLC) or gas chromatography, which often involves extensive and time‐consuming sample preparation, Raman or IR spectroscopy can avoid these procedures. The present work introduces a fast and reliable quantification method for the determination of naturally occurring indigo dye in dyer's knotweed (Polygonum tinctorium) based on Fourier transform (FT) Raman spectroscopy. The results were validated by HPLC‐UV, and the merits and drawbacks of the present method are elaborated. Besides the qualitative aspects of signal assignment and comparison to appropriate attenuated total reflectance Fourier transform infrared (ATR‐FT‐IR) measurements, the Raman spectrum of dihydro indigo, an important intermediate in the indigo dying process, is presented for the first time and discussed with regard to its spectroscopic behaviour. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectroscopic analysis of a dye–mineral composite–a Raman and FT‐IR study

In this investigation, we address the question of how organic thioindigo binds to inorganic palygorskite to form a pigment similar to Maya Blue. We also address how such binding, if it occurs, might be affected by varying the proportion of dye relative to that of the mineral, and by varying the length of heating time used in preparation of the pigment. In addition to samples of palygorskite and thioindigo both alone, four synthetic pigment samples were prepared; two samples of 8 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h, and two samples of 16 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h. All samples were examined using Fourier transform‐infrared (FT‐IR) and FT‐Raman spectroscopy. For the pigment samples, FT‐IR peaks at 1627 cm⁻¹ are attributed to a downshifted CO stretching mode of thioindigo due to dye–clay interaction. This interpretation is corroborated by FT‐Raman CO peaks with 14 cm⁻¹ shifts to lower wavenumber for the pigment relative to thioindigo alone. Additional Raman scattering between 550 cm⁻¹ and 650 cm⁻¹ also suggests dye–clay interaction through metal–oxygen bonding. We are thus led to the possibility of mostly hydrogen bonding between silanol and carbonyl at lower dye concentration, with a predominance of metal–oxygen bonding at higher dye concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

SERS and Raman imaging as a new tool to monitor dyeing on textile fibres

Textile fibres containing Ag nanoparticles have been widely explored for a number of antimicrobial fabrics. Moreover, it is well‐known that textile dyeing is a critical stage in the manufacture thereof. This research shows that surface enhanced Raman scattering (SERS) and Raman imaging can be used with advantage in the monitoring of this process. Using Ag containing linen fibres stained with methylene blue (MB), it was possible to map the local distribution of the MB dye in the fibres by Raman imaging. MB was selected as the SERS molecular probe and as a model dye. Composites of linen fibres and Ag nanoparticles were prepared by distinct methods and used as SERS substrates in order to evaluate the effect of the preparative method on the Raman images. Our results demonstrate that by using Raman imaging associated to the presence of Ag nanoparticles, it is possible to distinguish the local distribution of the dye on the textile surface. This investigation allows to foreseeing the use of this technique in terms of quality control of Ag containing fabrics, which is a market in great expansion. Copyright © 2016 John Wiley & Sons, Ltd.     

古代丝织品及古建彩画蓝色染料的微量及无损分析

染料分析是研究织物颜色老化变色的基础,同时对于了解我国印染工艺的发展有非常重要的作用。通过薄层色谱和拉曼光谱方法,对六个唐代丝绸样品的蓝色染料和故宫建福宫建筑彩画的蓝色物进行了分析,并对两种方法在文物上的适用性进行了比较。结果表明这些呈色物质均为靛蓝,靛蓝不仅作为染料被古人使用,也被当作颜料用于彩绘壁画,使用范围非常广范。两种分析的方法各有利弊,拉曼光谱是无损分析,薄层色谱需要样品量少,但可获得更多的信息。     

Raman of indigo on a silver surface. Raman and theoretical characterization of indigo deposited on silicon dioxide-coated and uncoated silver nanoparticles

Raman, surface-enhanced Raman scattering, and shell isolated nanoparticles-enhanced Raman scattering techniques were used to study the indigo–nanoparticle interaction nature. Silver nanoparticles were employed with and without a silicon dioxide spacer inert layer. The SERS spectral profile, obtained using silver nanoparticles, is different from the Raman one, which led to the proposition that the indigo–silver interaction is in the range of intermolecular interactions. SERS spectral reproducibility suggests identical organization and orientation of the analyte on the metal surface. The shell isolated nanoparticles enhanced Raman scattering spectrum of indigo, obtained by using silicon dioxide coated silver nanoparticles resulted similar to its Raman spectrum. This result indicates that the indigo structure is chemically unmodified by the silicon dioxide-coated silver surface. From the shell-isolated nanoparticles-enhanced Raman scattering experiments, the electromagnetic mechanism is proposed as the reason for the spectral enhancement. Theoretical calculations allow one to infer both the indigo–silver surface interaction nature and the orientation of indigo on the surface.     

Adsorptive parameters and influence of hot geometries on the SER(R) S spectra of methylene blue molecules adsorbed on gold nanocolloidal particles

The vibrational signatures of methylene blue (MB) dye molecule have been reported. Complete vibrational assignments of the molecule are presented for the first time. Concentration‐dependent surface enhanced resonance Raman scattering [SER(R) S] spectra of the molecule have been investigated. Fluorescence spectroscopic technique has been applied to explore the concentration of the probe molecule actually adsorbed on the gold nanocolloidal (AuNC) surface. The free energy of adsorption and saturated concentration of MB molecules on AuNC surface are also estimated. Gigantic enhancements ~10⁵–10¹³ orders of magnitude have been recorded for the enhanced Raman bands in the SER(R) S spectra. The possible orientation of the molecule on the AuNC surface and their probable protrusions within the hot spots have been suggested. The hot geometries and correlation between the plasmonic behavior of the nanoparticles and enhancement efficiencies of the SER(R) S band have been mapped with the aid of three‐dimensional finite difference time domain (3D‐FDTD) simulations. Application of soft lithographic technique to engineer the pattern formation of hetero dimeric spherical aggregates will be an interesting field of study in future to enhance the detection limit of this and similar types of dye molecules. Copyright © 2015 John Wiley & Sons, Ltd.     

Three fabricated pigments (Han purple,indigo and emerald green) in ancient Chinese artifacts studied by Raman microscopy,energy‐dispersive X‐ray spectrometry and polarized light microscopy

In this study, we analyzed three fabricated pigments from ancient artifacts in China. The purple pigment was obtained from a painted pottery figurine unearthed from the Chu Tombs group of the Western Han dynasty in Xuzhou, Jiangsu Province. The dark blue dye was from silk textiles in the Palace Museum. The green pigment was from decorative paintings on ancient architectures in the Palace Museum. These pigments were analyzed with Raman microscopy (RM), energy‐dispersive X‐ray (EDX) analytic spectroscopy and polarized light microscopy (PLM). By comparing their Raman spectra with standard samples, the primary ingredients of the purple pigment and the dark blue dye were found to be Han purple and indigo, respectively. However, the green pigment could not be identified by RM because of strong fluorescence. It was then confirmed to be emerald green by using EDX analytic microscopy and PLM. We also describe the traditional manufacturing methods of these pigments and their applications on artifacts in Chinese history. Copyright © 2007 John Wiley & Sons, Ltd.     

Synchrotron powder diffraction on Aztec blue pigments

Some samples of raw blue pigments coming from an archaeological rescue mission in downtown Mexico City have been characterized using different techniques. The samples, some recovered as a part of a ritual offering, could be assigned to the late Aztec period (XVth century). The striking characteristic of these samples is that they seem to be raw pigments prior to any use in artworks, and it was possible to collect a few μg of pigment after manual grain selection under a microscopy monitoring. All pigments are made of indigo, an organic colorant locally known as añil or xiuhquilitl. The colorant is always found in combination with an inorganic matrix, studied by powder diffraction. In one case the mineral base is palygorskite, a rare clay mineral featuring micro-channels in its structure, well known as the main ingredient of the Maya blue pigment. However, other samples present the minerals sepiolite (a clay mineral of the palygorskite family) and calcite. Another sample contains barite, a mineral never reported in prehispanic paints. We present the results of characterization using high resolution powder diffraction recorded at the European Synchrotron Radiation Facility (BM25A, SpLine beamline) complemented with other techniques. All of them gave consistent results on the composition. A chemical test on resistance to acids was done, showing a high resistance for the palygorskite and eventually sepiolite compounds, in good agreement with the excellent resistance of the Maya blue.     

Catalytic reduction of methylene blue by sulfide ions in the presence of nanoAlMCM-41 material

This article reports the reduction of methylene blue (MB) by sulfide ions (S²⁻) in aqueous solution by a nanoAlMCM-41 catalyst. The results obtained showed that, under acidic conditions (pH=2) MB was reduced to the Leuco methylene blue (LMB) form by sulfide ions and by changing the pH between 2.0 and 7.0 a reduction of the MB dye to the MBH₂⁺ form was observed. In alkaline media (pH=8), a reduction of methylene blue by sulfide ions to the MBH₂⁺ form and demethylation of the dye was observed simultaneously. The demethylation of MB leads to a thionine dye product. Using nanoAlMCM-41 but with encapsulated CoS nanoparticles only causes demethylation of MB in aqueous solution.     

Surface‐enhanced Raman scattering study of the red dye laccaic acid

FT‐Raman and surface‐enhanced Raman scattering (SERS) spectroscopy were applied to the study of lac dye, a highly fluorescent anthraquinone red dye. The SERS spectra were obtained at different pH values, on Ag nanoparticles prepared by chemical reduction with citrate and hydroxylamine, and at several excitation wavelengths, in order to find the best experimental conditions for the detection of the lac dye. The lower detection limit was achieved using nanoparticles prepared by reduction with hydroxylamine, excitation at 514.5 nm, and slightly acidic pH conditions, thus exploiting a combination of factors including lower electrostatic repulsion between dye and nanoparticles and resonance Raman enhancement. A comparison between the adsorption of laccaic acid (LA) and carminic acid (CA), another anthraquinone red dye, was also done, based on the SERS spectra of both dyes. Copyright © 2007 John Wiley & Sons, Ltd.     

One-step fabricated Fe3O4@C core–shell composites for dye removal: Kinetics,equilibrium and thermodynamics

B-Fe₃O₄@C core–shell composites were synthesized via one-pot hydrothermal carbonization (HTC) process and used as an adsorbent for the removal of methylene blue (MB) from aqueous solution. By using sodium borate as the catalyst, the hydrothermal carbonization process of B-Fe₃O₄@C core–shell composites was optimized and a higher surface area was obtained. The adsorbent was characterized by XRD, Raman spectra, SEM, TEM and N₂ adsorption/desorption isotherms. We studied the dye adsorption process at different conditions and analyzed the data by employing the Langmuir and Freundlich models, and the equilibrium data fitted well with both models. Kinetic analyses were conducted by using the Lagergren pseudo-first-order and pseudo-second-order model and the results showed that the adsorption process was more consistent with the pseudo-second-order kinetics. To better understand the dye adsorption process from the thermodynamics perspective, we also calculated ΔH^ο, ΔS^ο, ΔG^ο and E_a, the results suggesting that the MB adsorption process was physisorption endothermic process, and spontaneous at room temperature. The as-synthesized B-Fe₃O₄@C showing high magnetic sensitivity provides a facile and efficient way to recycle from aqueous solution.     

Adsorption of methylene blue onto sonicated sepiolite from aqueous solutions

The aim of the present study is to enhance the methylene blue (MB) adsorption of sepiolite by ultrasonic treatment. The natural sepiolite was pretreated by sonication to improve the surface characteristics and enhance the dye uptake capacity. Sonication process resulted in a significant increase in the specific surface area (SSA) of sepiolite. The FTIR spectrum of the sonicated sepiolite indicates that the tetrahedral sheet is probably distorted after sonication process. The effect of various parameters such as sonication, pH, initial dye concentration and temperature on dye adsorption has been investigated. The adsorbed amount of MB on sepiolite increased after sonication as well as with increasing pH and temperature. The experimental data were evaluated by applying the pseudo-first- and second-order, and the intraparticle diffusion adsorption kinetic models. Adsorption process of MB onto sepiolite followed the pseudo-second-order rate expression. The experimental data were analyzed by Langmuir and Freundlich isotherms, and found that the isotherm data were reasonably well correlated by Langmuir isotherm. Maximum monolayer adsorption capacity of sepiolite for MB increased from 79.37 to 128.21 mg/g after the sonication. Various thermodynamic parameters, such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated. The thermodynamics of MB/sepiolite system indicated spontaneous and endothermic nature of the process. Adsorption measurements showed that the process was very fast and physical in nature.     

Preparation of mesoporous poly (acrylic acid)/SiO2 composite nanofiber membranes having adsorption capacity for indigo carmine dye

Mesoporous poly (acrylic acid)/SiO₂ (PAA/SiO₂) composite nanofiber membranes functionalized with mercapto groups were fabricated by a sol-gel electrospinning method, and their adsorption capacity for indigo carmine was investigated. The membranes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, x-ray powder diffraction (XRD), and nitrogen adsorption–desorption measurement. SEM and TEM observation results showed that the PAA/SiO₂ fibers had diameters between 400–800 nm and mesopores with an average pore size of 3.88 nm. The specific surface area of the mesoporous nanofiber membranes was 514.89 m²/g. The characteristic peaks for mercapto group vibration in FTIR and Raman spectra demonstrated that the mercapto groups have been incorporated into the silica skeleton. The adsorption isotherm data of indigo carmine on the membranes fit well with Redlich–Peterson model, and the maximum adsorption capacity calculated was 523.11 mg/g. It was found that the removal rate of indigo carmine by the membranes reached a maximum of 98% in 90 min and the adsorption kinetics followed a pseudo-second-order model. The high adsorption capacity of PAA/SiO₂ nanofiber membrane makes it a promising adsorbent for indigo carmine removal from the wastewater.     

Raman and surface enhanced Raman scattering of a black dyed silk

The Raman and surface enhanced Raman scattering (SERS) spectra of a black dyed silk sample (BDS) were registered. The spectral analysis was performed on the basis of Raman and SERS spectral data of isolated samples of Bombyx mori silk fibroin, its motif peptide component (GAGAGS) and the synthetic reactive black 5 dye (RB5). The macro FT‐Raman spectrum of the silk sample is consistent with a silk II‐Cp crystalline fraction of Bombyx mori silk fibroin; the SERS spectrum is highly consistent with conformational modifications of the fibroin due to the interactions with the Ag nanoparticles. The GAGAGS peptide sequence dominates the Raman spectrum of the silk. The SERS spectrum of the peptide suggests a random coil conformation imposed by the surface interaction; the serine residue in the new conformation is exposed to the surface. Quantum chemical calculations for a model of the GAGAGS–Ag surface predict a nearly extended conformation at the Ag surface. The Raman spectrum of the dye was analysed, and a complete band assignment was proposed; it was not possible to propose a preferential orientation or organization of the molecule on the metal surface. Quantum chemical calculations for a model of the dye interacting with a silver surface predict a rather coplanar orientation of the RB5 on the Ag metal surface. The Raman spectrum of the BDS sample is dominated by signals from the dye; the general spectral behaviour indicates that the dye mainly interacts with the silk through the sulphone (–SO₂–) and sulphonate (–SO₂–O–) groups. Besides the presence of dye signals, mainly ascribed to the sulphone and sulphonate bands, the SERS spectrum of the BDS sample also displays bands belonging to the amino acids alanine, glycine, serine and particularly tyrosine. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of biotite content of hydrogels on enhanced removal of methylene blue from aqueous solution

A series of chitosan-g-poly(acrylic acid)/biotite (CTS-g-PAA/BT) hydrogels with unique clay biotite (BT) were prepared and used to remove cationic dye methylene blue (MB) from aqueous solution by batch adsorption experiments. Variables of the system including BT content, initial pH, contact time, initial concentration, and temperature affecting the adsorption efficiency of MB by CTS-g-PAA/BT hydrogels were investigated. Kinetic studies indicated that the adsorption data well followed pseudo-second-order kinetics. Langmuir and Freundlich isotherm models were applied to experimental equilibrium data of MB adsorption depending on temperature. The adsorption equilibrium data obeyed Langmuir isotherm, and the monolayer adsorption capacity calculated from the Langmuir isotherm was 2,125.70 mg/g for CTS-g-PAA/10% BT at 30 °C. The adsorption capacity was much higher compared with other hydrogels with the same content of other clays. The introduction of BT into the hydrogel could effectively improve its adsorption properties and reduce the cost. Thermodynamic parameters were evaluated for the dye-adsorbent systems and revealed that the adsorption process was spontaneous and exothermic in nature. All the information gave an indication that CTS-g-PAA/10% BT could potentially be applied as an efficient adsorbent for cationic dye removal from aqueous solution.     

Optimization of the ultrasonic assisted removal of methylene blue by gold nanoparticles loaded on activated carbon using experimental design methodology

The present study was focused on the removal of methylene blue (MB) from aqueous solution by ultrasound-assisted adsorption onto the gold nanoparticles loaded on activated carbon (Au-NP-AC). This nanomaterial was characterized using different techniques such as SEM, XRD, and BET. The effects of variables such as pH, initial dye concentration, adsorbent dosage (g), temperature and sonication time (min) on MB removal were studied and using central composite design (CCD) and the optimum experimental conditions were found with desirability function (DF) combined response surface methodology (RSM). Fitting the experimental equilibrium data to various isotherm models such as Langmuir, Freundlich, Tempkin and Dubinin–Radushkevich models show the suitability and applicability of the Langmuir model. Analysis of experimental adsorption data to various kinetic models such as pseudo-first and second order, Elovich and intraparticle diffusion models show the applicability of the second-order equation model. The small amount of proposed adsorbent (0.01 g) is applicable for successful removal of MB (RE > 95%) in short time (1.6 min) with high adsorption capacity (104–185 mg g⁻¹).     

Raman Microspectroscopic Analysis of Polychrome Wooden Artifact from the Astana Tomb of the Tang Dynasty,Xinjiang, ChinaEI北大核心CSCD

The Turpan District is characterized by a typical dry climate, so that many organic relics have been well preserved. A piece of wooden artifact with 9 colors was unearthed from Astana graveyard which is rich in cultural connotations. In the present paper, Raman microscopy was employed for in-situ, nondestructive analysis of pigments that remained on this artifact, and many mineral pigments (gypsum, red lead, carbon black, haematite, atacamite) and vegetable dyes (gamboges and indigo) were identified. It is noteworthy that this is the earliest example that gamboges were used as yellow dye in China at present. The results show that the Gaochang people had mastered skills proficiently, including the preparation, deployment and usage of pigment. The investigation of pigments could provide a basis for the restoration and conservation of relics, and more evidence for pigments trade business and cultural exchanges.