Sensing colorimetric approaches based on gold and silver nanoparticles aggregation: Chemical creativity behind the assay. A review

Localized surface plasmon resonance (LSPR) is one of the most remarkable features of gold nanoparticles (Au NPs) and silver nanoparticles (Ag NPs). Due to these inherent optical properties, colloidal solutions of Au and Ag NPs have high extinction coefficients and different colour in the visible region of the spectrum when they are well-spaced in comparison with when they are aggregated. Therefore, a well-designed chemical interaction between the analyte and NPs surroundings leads to a change of colour (red to blue for Au NPs and yellow to brown for Ag NPs from well-spaced to aggregated ones, respectively) allowing the visual detection of the target analyte.     

Some new trends in the ionoluminescence of minerals

Ionoluminescence (IL) has mainly been used to detect impurities or defects inside synthetic materials. This paper gives a summary of new applications of IL to natural minerals that might be found in ancient pieces of jewellery or decorative artefacts (affreschi, stucchi, mosaics). Some relevant examples of its use for archaeometrical purposes are given to highlight the potential of the technique. Chemical information can be obtained by luminescent characterization of minerals. IL spectra act as digital imprint for elements or defects inside each material, enabling differentiation of natural specimens from imitations and/or synthetic analogues. Crystal field theory indicates it is the coordination number of the emitter inside the crystalline structure that gives information on its valence. Historical confusion between rubies and red spinel can easily be resolved by analysis of IL spectra. Modern synthetic diamonds can also be discriminated and blue sapphire can be distinguished from blue kyanite, a silicate that is currently being sold as its imitation. The technique can also differentiate between the synthetic and the natural gems. Polymorphs can be identified, and it is possible to recognize minerals from isomorphic series (from the same chemical group with the same structure) even when they share the same light emitter (e.g. Mn²⁺, in carbonates). High-quality glasses (e.g. laser glasses) which are normally used for faking gemstones can be also detected. We fully believe IL will, in the future, be a powerful technique for determining the crystallinity of solids. This paper gives an overview of possible applications of IL to archaeometry for mineral characterization; this is a new application that still requires further study.     

The role of crosslinking and polarity in the dark relaxation of azobenzene-based,polymer-stabilised cholesteric liquid crystals

Prior examinations have reported that polymer stabilisation of azobenzene-based cholesteric liquid crystal (CLC) mixtures can reduce the time necessary for complete colour restoration in the dark from three days to as few as five minutes. This work extends upon these prior examinations by exploring and elucidating the role of crosslinker concentration and monomer polarity on the colour restoration of a representative CLC mixture composed of a high HTP bis(azo) binapthanyl chiral dopant (QL76) mixed into the cyanobiphenyl nematic liquid crystal host MDA-00-1444. The impact of these variables was unexpectedly convoluted. In all the formulations examined here, polymer stabilisation dramatically reduces the time for complete colour restoration of the starting reflection notch. In mixtures based on nonpolar liquid crystal monomers, increasing the crosslinker concentration reduces the time necessary for complete colour restoration. However, the dependence on crosslinker concentration reverses in mixtures composed from polar liquid crystal monomers in which increasing the crosslinker concentration serves to increase the time necessary for complete colour restoration.     

Tracking nitrogen-to-nickel ratio and prevalent paramagnetic species in synthetic diamonds by electron spin resonance at 90 K

Nitrogen and nickel are the main impurities in the type Ib synthetic diamonds obtained under high pressure and high temperature conditions using nickel-containing catalysts. Nitrogen enters the synthesized diamond from the air. The nickel/nitrogen ratio for the two types of diamonds, obtained with and without an aluminum getter that prevents the diamond crystal lattice from nitrogen penetration, was studied by electron spin resonance at 90 K.     

Phase modulation using different orientations of a chiral nematic in liquid crystal over silicon devices

Modulation of the intensity of light by high quality reflective micro-displays is predominantly carried out by liquid crystal over silicon (LCoS) spatial light modulator (SLM) technology for applications such as pico-projectors. Wider use of these devices, in applications such as computer-generated holography and optical correlation, is limited by their phase modulation ability and illumination polarisation state dependence. These devices rely on planar or twisted nematic liquid crystals to modulate the light, but due to their viscoelastic properties they are inherently slow. Research into the use of the polymer stabilised blue phase has already shown that it can offer high speed phase modulation. However, other chiral nematic orientations are yet to be compared in LCoS devices. In this article, we demonstrate that polymer-stabilised chiral nematic liquid crystal electro-optical effects can offer phase modulation in silicon backplane devices. The uniform standing helix and focal conic textures are shown to be independent of the input light polarisation state and the uniform lying helix is shown to be polarisation dependent. These optical responses are then compared with that of the blue phase to identify a suitable orientation for further development in LCoS technology in order to find a high-speed, full phase modulating material.     

The Nature of the Colour Centres in ‘Maya Blue’ — the Incorporation of Organic Pigment Molecules into the Palygorskite Lattice

It is shown by optical spectroscopy that indigo molecules, most likely incorporated into the channels of the palygorskite host structure, are the solely colour centres in the ancient Maya Blue pigment — in use during the Maya cultural period in Yucatan and Guatemala. This study also shows that the blue colour of solid indigo shifts toward turquoise and greenish hues when fastened to the host; it is suggested that the corresponding spectral modifications originate from the energy when single indigo molecules undergo hydrogen bonding with the hydroxy‐groups in the channels (or in the open channels on the surface). Indeed artefacts from the Maya culture exhibit rather greenish than pure blue colours. Similarly a tetrachloro‐derivative of thioindigo forms hydrogen bonds with palygorskite, as evidenced by an again distinct colour change from red‐violet to blueish‐violet. Bulkier pigment molecules bearing hydroxy‐groups, such as anthrachinon derivatives, seem to directly react with the host surface, but without producing very significant colour shifts.     

Cholesteric liquid crystal displays as optical sensors of barbiturate binding

The influence on the optical properties of cholesteric liquid crystal displays (LCDs) was examined for neutral molecule binding by mesogen/receptors in the mesomorphic phase. The motivation was to prepare neutral molecule sensors that use a colour change to signal analyte binding. A receptor that binds barbiturate analytes was modified with two or one cholesteryl groups to yield compounds 2 and 3, respectively. LCDs were prepared by incorporating one of the receptor/mesogen compounds into a cholesteric LC blend along with a potential H‐bonding guest. The optical properties of the LCDs were then determined by measuring the absorbance of the displays. For various LCDs, the colour of the display depended upon several factors: the amount of guest molecule used, the number of cholesteryl side chains on the receptor and the mole concentration of receptor/mesogen in the blend. In particular, complementary host/guest binding of H‐bonding analytes by the bis(cholesteryl) receptor 2 in a cholesteric LCD caused a change of up to +70 nm, which was observed by the naked eye as a blue‐to‐orange colour change. Control experiments confirm that the colour of an LCD is a consequence of molecular recognition in the mesomorphic phase.     

Characterisation of diamond coatings with different morphologies by Raman spectroscopy using various laser wavelengths

Since the beginning of low-pressure diamond synthesis, Raman spectroscopy has been widely used to identify and characterise the quality of diamonds. The diamond crystal is characterised by a Raman peak at about 1,332 cm^-1. Other peaks are associated with miscellaneous carbon structures, e.g. graphite and amorphous phases. In recent years, both well-faceted crystalline diamonds and nanocrystalline and ultrananocrystalline diamonds have been investigated. For these fine-grained materials, the diamond peak at 1,332 cm^-1 disappears and the intensities of peaks at other wavelengths increase. To study the influence of the Raman laser wavelength, three lasers were used (472.681 nm, blue; 532.1 nm, green; 632.81 nm, red). For well-faceted diamonds, the Raman spectra with blue and green laser light were similar. A shift of the peak maxima and different intensities were observed. With use of the red laser, a strong luminescence peak and low peak intensities for the various carbon-related peaks occurred. When the diamond morphology changes from well-faceted to fine-grained ballas diamond, the spectra are similar for all three lasers.     

Chemical Investigation of Coloured Minerals in Natural Stones of Commercial Interest

The economic interest in natural stones provides an interesting input to the study of coloured rock-forming minerals. Generally, the colour of a mineral is attributed either to the presence of intrinsically-coloured constituents or of trace elements substituting major elements in the crystallographic sites, or to physical factors such as crystal lattice defects. We have analysed the blue and blue-green silicate minerals dumortierite and amazonite, coming from Mozambique quartzites, and from Malawi and Brazil granitoids, respectively. This study was performed by a multiple analytical approach including (a) a comparison of different signals (optical light-polarized images, backscattered electron images and X-ray multielemental maps); and (b) a collection of quantitative data obtained by WDS systems for major elements, and by WDS and/or micro-PIXE facility for trace elements. A good correlation between Ti concentration zoning and pleochroism variations was observed in dumortierite. In addition, the blue dumortierite of Mozambique, with its unusual significant amounts of antimony (about 5 wt.% Sb₂O₃), represents a mineral with an intermediate composition between dumortierite and holtite. In amazonite the aquamarine colour seems to be related to the Pb content on the order of some hundreds of ppm.     

Critical study of metallochromic indicators for calcium

The visual clarity of the colour changes at the end-points in the compleximetric titration of calcium is discussed for the metallochromic indicators, arsenazo-III, calcein, calcon, eriochrome blue black B, methylthymol blue, murexide, phthalein complexone, and thymolphthalein complexone. The colour changes were specified with the help of CIE chromaticity diagrams. The sharpness of the colour changes of the indicators was studied by varying the optical (or colour) concentration. Thymolphtalein complexone and phthalein complexone are shown to be the most appropriate indicators for the visual titration of calcium with EDTA.     

Reflective blue phase liquid crystal displays with double-side concave-curved electrodes

Reflective blue phase liquid crystal display (BPLCD) is a promising candidate for field sequential colour displays with reflective liquid-crystal-on-silicon (LCoS). However, the issue of high operation voltage still hinders its widespread applications. We propose a reflective BPLCD with double-side concave-curved electrode and research its operation voltage and electro-optic characteristics in simulation, which is compared to the transmissive mode. The effect of double-side electrodes on horizontal electric field and operation voltage is analysed. The improvement of concave-curved electrodes on reflectance is discussed. A reflective BPLCD has two times the optical path difference compared to the transmissive mode. By using double-side concave-curved electrodes, the reflectance increased by 23% and the operation voltage reduced by 32% compared to the traditional in-plane switching mode. This work enables BPLC to be integrated with reflective LCoS.     

Photochromic reverse mode polymer dispersed liquid crystals

Control of light intensity and colour are two of the major features required in the realization of smart windows. We designed a bi‐functional polymer dispersed liquid crystal (PDLC) film in order to satisfy such requirements, i.e. it is able both to modulate the optical transmission, if an external electric field is applied, and to change colour if exposed to sunlight. A monomer/liquid crystal mixture was doped with a small amount of photochromic material and homeotropically aligned by means of rough surfaces. A transparent and pale pink coloured film was achieved after photopolymerization. Such a film changes colour upon exposure for some seconds to sunlight or ultraviolet radiation in a persistent but reversible manner. In addition, the film appears transparent without the application of an electric field (OFF state) and becomes opaque on application of a driving voltage of about 75?V (ON state), and thus the film operates in reverse mode with respect to conventional PDLCs.     

Photochromic reverse mode polymer dispersed liquid crystals

Control of light intensity and colour are two of the major features required in the realization of smart windows. We designed a bi-functional polymer dispersed liquid crystal (PDLC) film in order to satisfy such requirements, i.e. it is able both to modulate the optical transmission, if an external electric field is applied, and to change colour if exposed to sunlight. A monomer/liquid crystal mixture was doped with a small amount of photochromic material and homeotropically aligned by means of rough surfaces. A transparent and pale pink coloured film was achieved after photopolymerization. Such a film changes colour upon exposure for some seconds to sunlight or ultraviolet radiation in a persistent but reversible manner. In addition, the film appears transparent without the application of an electric field (OFF state) and becomes opaque on application of a driving voltage of about 75 V (ON state), and thus the film operates in reverse mode with respect to conventional PDLCs.     

白光LED用Ce:YAG单晶的光学性能与掺杂浓度分析

采用提拉法生长Ce∶YAG单晶,通过X射线衍射和激发发射光谱对其晶相结构和光谱特性进行了表征,研究了Ce∶YAG单晶封装白光LED的最佳掺杂浓度.在455 nm蓝光激发下,Ce∶YAG单晶的发射光谱可由中心波长526 nm(5d12E gГ8g→4f12F7/2Г8u)的宽发射带(500~650 nm)组成;激发光谱由343 nm(4f12F5/2Г7u→5d1 2E gГ7g)和466 nm(4f12F5/2Г7u→5d1 2E gГ8g)2个激发峰组成;Stokes位移为2448 cm-1,Huang-Rhys因子为6.12.研究结果表明,Ce∶YAG单晶中Ce离子掺杂浓度与封装的白光LED之间有对应关系,在650 nm红粉调节下Ce离子最佳掺杂浓度范围为0.034~0.066.     

The use of vanadium-sulphosalicylic acid complex as a redox indicator

In a previous communication it was reported that vanadium^V gives an intense turquoise-blue colour with sulphosalicylic acid in concentrated sulphuric acid and that the colour reaction is specific and very sensitive for the detection of vanadium^V. During our studies on the nature of the complex, it was found that vanadium^IV gives a negative colour test and that the blue colour developed by the reagent with vanadium^V is discharged on the addition of a reducing agent like iron^II, uranium^IV or hydroquinone. It was also observed that the blue colour is restored by the addition cerium^IV solution. This reversible property of the complex has been further investigated to see if the complex can be used as a redox indicator.     

The photoluminescence of Co-Al-layered double hydroxide

We report a new optical behaviour of pure Co-Al-layered double hydroxide (LDH).It was found that the Co-Al-LDH sample could emit fluorescence without any fluorescent substances intercalated.Its excitation spectrum shows a maximum peak near the wavelength 370nm,the maximum emission peak appears at 430 nm and the photoluminescence colour of the Co-Al-LDH sample is blue.This new optical property will be expected to extend the potential applications of LDHs in optical materials field.     

Micro-analytical evidence of origin and degradation of copper pigments found in Bohemian Gothic murals

Correct identification of pigments and all accompanying phases found in colour layers of historical paintings are relevant for searching their origin and pigment preparation pathways and for specification of their further degradation processes. We successfully applied the analytical route combining non-destructive in situ X-ray fluorescence analyses with subsequent laboratory investigation of micro-samples by optical microscopy, scanning electron microscopy/energy-dispersive spectroscopy and X-ray powder micro-diffraction (micro-XRD) to obtain efficiently all the data relevant for mineralogical interpretations of the copper pigments origin. Cu salts (carbonates, chlorides, sulphates, etc.) used as pigments exist in a range of polymorphs with similar or identical composition. The efficiency of the micro-XRD for direct identification of such crystal phases present in micro-samples of colour layers was demonstrated in the presented paper. A new, until now unpublished, type of copper pigment—cumengeite, Pb₂₁Cu₂₀Cl₄₂(OH)₄₀—used as a blue pigment on a sacral wall painting in the Czech Republic was found by means of micro-XRD. Furthermore, azurite, malachite, paratacamite, atacamite and posnjakite were identified in fragments of colour layers of selected Gothic wall paintings. We found Cu–Zn arsenates indicating the natural origin of azurite and malachite; artificial malachite was distinguishable according to its typical spherulitic crystals. The corrosion of blue azurite to green basic Cu chloride was clearly evidenced on some places exposed to the action of salts and moisture—in a good agreement with the results of laboratory experiments, which also show that oxalic acid accelerates the corrosion of Cu pigments.     

Natural diamonds—Major,minor and trace impurities in relation to source and physical properties

Nuclear techniques for the determination of 39 impurity elements in diamonds are described. A common impurity chemistry was found for different diamonds and is considered to reflect the composition of the magma from which they crystallised. A relatively successful attempt was made to differentiate between diamonds from three different kimberlites by the application of discriminant analysis.     

High-Reflective Templated Cholesteric Liquid Crystal Filters

Cholesteric liquid crystals (CLCs) have been widely applied in optical filters due to Bragg reflection caused by their helical structure. However, the reflectivity of CLC filters is relatively low, commonly less than 50%, as the filters can only reflect light polarized circularly either left- or right-handedly. Therefore, a high-reflective CLC filter with a single-layer template was proposed which may reflect both right- and left-handed polarized light. The CLC filters of the red, green, blue color were fabricated by the templating technology, which show good wavelength consistency. Additionally, a multi-phase liquid crystal filter with high reflectance was demonstrated by the single-layer templating technology. The templated CLC or multi-phase liquid crystal filters show great potential applications in the optical community, reflective display, and lasing.     

ZnSe colloidal nanoparticles synthesized by solvothermal method in the presence of ZrCl4

The nanocrystalline ZnSe was synthesized from precursors of zinc acetate and Se powder in a high boiling trioctylphosphine (TOP), oleic acid, and ZrCl(4) by solvothermal method. The produced ZnSe nanoparticles showed gradual absorption edge shifting towards blue wavelength region as well as transformation of crystal phase from cubic to hexagonal with increasing ZrCl(4) concentrations in precursor solutions. The particle size calculated from XRD measurements for ZnSe nanoparticles was decreased with increasing ZrCl(4) concentrations for a reaction time of 240 min, from 6.5 nm to 5.1 nm whereas from TEM measurements it was 7.0 to 6.1 nm at 0.0 and 22.5 mol% of ZrCl(4), respectively. No trace of zirconium was found in solid ZnSe nanoparticles by SEM-EDS analysis but the atomic percentage of Se with respective to Zn was decreased with increasing ZrCl(4). The absorption edge blue shifting was explained on the basis of decreased particle size. The crystal phase transformation may be due to the combined effect of small internal energy difference between the two phases and the decrease of crystallite size.