N-Aryl stilbazolium dyes as sensitizers for solar cells

Eight new N-arylstilbazolium chromophores with electron donating –NR2 (R = Me or Ph) substituents have been synthesized via Knoevenagel condensations and isolated as their PF6− salts. These compounds have been characterized by using various techniques including 1H NMR and IR spectroscopies and electrospray mass spectrometry. UV–vis absorption spectra recorded in acetonitrile are dominated by intense, low energy π → π* intramolecular charge-transfer (ICT) bands, and replacing Me with Ph increases the ICT energies. Cyclic voltammetric studies show irreversible reduction processes, together with oxidation waves that are irreversible for R = Me, but reversible for R = Ph. Single crystal X-ray structures have been determined for three of the methyl ester-substituted stilbazolium salts and for the Cl− salts of their picolinium precursors. Time-dependent density functional theory calculations afford reasonable predictions of ICT energies, but greater rigour is necessary for –NPh2 derivatives. The four new acid-functionalized dyes give moderate sensitization efficiencies (ca. 0.2%) when using TiO2-based photoanodes, with relatively higher values for R = Ph vs Me, while larger efficiencies (up to 0.8%) are achieved with ZnO substrates.

Comparative study on adsorption of two cationic dyes by milled sugarcane bagasse

Adsorptions of Rhodamine B (RhB) and Basic Blue 9 (BB9, also known as methylene blue) by sugarcane bagasse of different surface areas were compared in this study. There was a small gain in the amount of dye removed by increasing bagasse surface area from 0.57 m2/g to 1.81 m2/g. BB9 adsorption was less sensitive to surface area change than RhB adsorption. Adsorption capacity of 250 mg/L RhB on 1 g/L bagasse was 65.5 mg/g compared to a value of 30.7 mg/g obtained with BB9 under the same conditions. Increasing adsorption temperature (from 30 °C to 50 °C) while having no effect on RhB adsorption, slightly decreased BB9 adsorption by ~4%. The differences in adsorption performances between these dyes have been related to the molecular structure of the dyes and the surface chemistry of bagasse.

Synthesis, photophysical and electrochemical properties of aza-boron-diquinomethene complexes

A series of aza-boron-diquinomethene (aza-BODIQU) complexes with different aryl-substituents (B1–B6) were synthesized and characterized. Their photophysical properties were investigated systematically via spectroscopic and theoretical methods. All complexes exhibit strong 1π–π* absorption bands and intense fluorescent emission bands in the visible spectral region at room temperature. The fluorescence spectra in solution show the mirror image features of the S0→S1 absorption bands, which can be assigned to the 1π–π*/1ICT (intramolecular charge transfer) emitting states. Except for B6, all complexes exhibit high photoluminescence quantum yields (ΦPL = 0.47–0.93). The spectroscopic studies and theoretical calculations indicate that the photophysical properties of these aza-BODIQUs can be tuned by the appended aryl-substituents, which would be useful for rational design of boron–fluorine complexes with high emission quantum yield for organic light-emitting applications.

Near-infrared spectroscopic studies of human scalp hair in a forensic context

Human hair is a relatively inert biopolymer and can survive through natural disasters. It is also found as trace evidence at crime scenes. Previous studies by FTIRMicrospectroscopy and – Attenuated Total Reflectance (ATR) successfully showed that hairs can be matched and discriminated on the basis of gender, race and hair treatment, when interpreted by chemometrics. However, these spectroscopic techniques are difficult to operate at- or on-field. On the other hand, some near infrared spectroscopic (NIRS) instruments equipped with an optical probe, are portable and thus, facilitate the on- or at –field measurements for potential application directly at a crime or disaster scene. This thesis is focused on bulk hair samples, which are free of their roots, and thus, independent of potential DNA contribution for identification. It explores the building of a profile of an individual with the use of the NIRS technique on the basis of information on gender, race and treated hair, i.e. variables which can match and discriminate individuals. The complex spectra collected may be compared and interpreted with the use of chemometrics. These methods can then be used as protocol for further investigations. Water is a common substance present at forensic scenes e.g. at home in a bath, in the swimming pool; it is also common outdoors in the sea, river, dam, puddles and especially during DVI incidents at the seashore after a tsunami. For this reason, the matching and discrimination of bulk hair samples after the water immersion treatment was also explored. Through this research, it was found that Near Infrared Spectroscopy, with the use of an optical probe, has successfully matched and discriminated bulk hair samples to build a profile for the possible application to a crime or disaster scene. Through the interpretation of Chemometrics, such characteristics included Gender and Race. A novel approach was to measure the spectra not only in the usual NIR range (4000 – 7500 cm-1) but also in the Visible NIR (7500 – 12800 cm-1). This proved to be particularly useful in exploring the discrimination of differently coloured hair, e.g. naturally coloured, bleached or dyed. The NIR region is sensitive to molecular vibrations of the hair fibre structure as well as that of the dyes and damage from bleaching. But the Visible NIR region preferentially responds to the natural colourants, the melanin, which involves electronic transitions. This approach was shown to provide improved discrimination between dyed and untreated hair. This thesis is an extensive study of the application of NIRS with the aid of chemometrics, for matching and discrimination of bulk human scalp hair. The work not only indicates the strong potential of this technique in this field but also breaks new ground with the exploration of the use of the NIR and Visible NIR ranges for spectral sampling. It also develops methods for measuring spectra from hair which has been immersed in different water media (sea, river and dam)

Ocular surface changes with short-term contact lens wear

Contact lenses are a common method for the correction of refractive errors of the eye. While there have been significant advancements in contact lens designs and materials over the past few decades, the lenses still represent a foreign object in the ocular environment and may lead to physiological as well as mechanical effects on the eye. When contact lenses are placed in the eye, the ocular anatomical structures behind and in front of the lenses are directly affected. This thesis presents a series of experiments that investigate the mechanical and physiological effects of the short-term use of contact lenses on anterior and posterior corneal topography, corneal thickness, the eyelids, tarsal conjunctiva and tear film surface quality. The experimental paradigm used in these studies was a repeated measures, cross-over study design where subjects wore various types of contact lenses on different days and the lenses were varied in one or more key parameters (e.g. material or design). Both, old and newer lens materials were investigated, soft and rigid lenses were used, high and low oxygen permeability materials were tested, toric and spherical lens designs were examined, high and low powers and small and large diameter lenses were used in the studies. To establish the natural variability in the ocular measurements used in the studies, each experiment also contained at least one “baseline” day where an identical measurement protocol was followed, with no contact lenses worn. In this way, changes associated with contact lens wear were considered in relation to those changes that occurred naturally during the 8 hour period of the experiment. In the first study, the regional distribution and magnitude of change in corneal thickness and topography was investigated in the anterior and posterior cornea after short-term use of soft contact lenses in 12 young adults using the Pentacam. Four different types of contact lenses (Silicone hydrogel/ Spherical/–3D, Silicone Hydrogel/Spherical/–7D, Silicone Hydrogel/Toric/–3D and HEMA/Toric/–3D) of different materials, designs and powers were worn for 8 hours each, on 4 different days. The natural diurnal changes in corneal thickness and curvature were measured on two separate days before any contact lens wear. Significant diurnal changes in corneal thickness and curvature within the duration of the study were observed and these were taken into consideration for calculating the contact lens induced corneal changes. Corneal thickness changed significantly with lens wear and the greatest corneal swelling was seen with the hydrogel (HEMA) toric lens with a noticeable regional swelling of the cornea beneath the stabilization zones, the thickest regions of the lenses. The anterior corneal surface generally showed a slight flattening with lens wear. All contact lenses resulted in central posterior corneal steepening, which correlated with the relative degree of corneal swelling. The corneal swelling induced by the silicone hydrogel contact lenses was typically less than the natural diurnal thinning of the cornea over this same period (i.e. net thinning). This highlights why it is important to consider the natural diurnal variations in corneal thickness observed from morning to afternoon to accurately interpret contact lens induced corneal swelling. In the second experiment, the relative influence of lenses of different rigidity (polymethyl methacrylate – PMMA, rigid gas permeable – RGP and silicone hydrogel – SiHy) and diameters (9.5, 10.5 and 14.0) on corneal thickness, topography, refractive power and wavefront error were investigated. Four different types of contact lenses (PMMA/9.5, RGP/9.5, RGP/10.5, SiHy/14.0), were worn by 14 young healthy adults for a period of 8 hours on 4 different days. There was a clear association between fluorescein fitting pattern characteristics (i.e. regions of minimum clearance in the fluorescein pattern) and the resulting corneal shape changes. PMMA lenses resulted in significant corneal swelling (more in the centre than periphery) along with anterior corneal steepening and posterior flattening. RGP lenses, on the other hand, caused less corneal swelling (more in the periphery than centre) along with opposite effects on corneal curvature, anterior corneal flattening and posterior steepening. RGP lenses also resulted in a clinically and statistically significant decrease in corneal refractive power (ranging from 0.99 to 0.01 D), large enough to affect vision and require adjustment in the lens power. Wavefront analysis also showed a significant increase in higher order aberrations after PMMA lens wear, which may partly explain previous reports of "spectacle blur" following PMMA lens wear. We further explored corneal curvature, thickness and refractive changes with back surface toric and spherical RGP lenses in a group of 6 subjects with toric corneas. The lenses were worn for 8 hours and measurements were taken before and after lens wear, as in previous experiments. Both lens types caused anterior corneal flattening and a decrease in corneal refractive power but the changes were greater with the spherical lens. The spherical lens also caused a significant decrease in WTR astigmatism (WRT astigmatism defined as major axis within 30 degrees of horizontal). Both the lenses caused slight posterior corneal steepening and corneal swelling, with a greater effect in the periphery compared to the central cornea. Eyelid position, lid-wiper and tarsal conjunctival staining were also measured in Experiment 2 after short-term use of the rigid and SiHy contact lenses. Digital photos of the external eyes were captured for lid position analysis. The lid-wiper region of the marginal conjunctiva was stained using fluorescein and lissamine green dyes and digital photos were graded by an independent masked observer. A grading scale was developed in order to describe the tarsal conjunctival staining. A significant decrease in the palpebral aperture height (blepharoptosis) was found after wearing of PMMA/9.5 and RGP/10.5 lenses. All three rigid contact lenses caused a significant increase in lid-wiper and tarsal staining after 8 hours of lens wear. There was also a significant diurnal increase in tarsal staining, even without contact lens wear. These findings highlight the need for better contact lens edge design to minimise the interactions between the lid and contact lens edge during blinking and more lubricious contact lens surfaces to reduce ocular surface micro-trauma due to friction and for. Tear film surface quality (TFSQ) was measured using a high-speed videokeratoscopy technique in Experiment 2. TFSQ was worse with all the lenses compared to baseline (PMMA/9.5, RGP/9.5, RGP/10.5, and SiHy/14) in the afternoon (after 8 hours) during normal and suppressed blinking conditions. The reduction in TFSQ was similar with all the contact lenses used, irrespective of their material and diameter. An unusual pattern of change in TFSQ in suppressed blinking conditions was also found. The TFSQ with contact lens was found to decrease until a certain time after which it improved to a value even better than the bare eye. This is likely to be due to the tear film drying completely over the surface of the contact lenses. The findings of this study also show that there is still a scope for improvement in contact lens materials in terms of better wettability and hydrophilicity in order to improve TFSQ and patient comfort. These experiments showed that a variety of changes can occur in the anterior eye as a result of the short-term use of a range of commonly used contact lens types. The greatest corneal changes occurred with lenses manufactured from older HEMA and PMMA lens materials, whereas modern SiHy and rigid gas permeable materials caused more subtle changes in corneal shape and thickness. All lenses caused signs of micro-trauma to the eyelid wiper and palpebral conjunctiva, although rigid lenses appeared to cause more significant changes. Tear film surface quality was also significantly reduced with all types of contact lenses. These short-term changes in the anterior eye are potential markers for further long term changes and the relative differences between lens types that we have identified provide an indication of areas of contact lens design and manufacture that warrant further development.

Synthetic reevesite-like material as a visible light photocatalyst for the decontamination of water

A synthetic reevesite-like material has been shown to decolorize selected dyes and degrade phenolic contaminants photocatalytically in water when irradiated with visible light. This material can photoactively decolorize dyes such as bromophenol blue, bromocresol green, bromothymol blue, thymol blue and methyl orange in less than 15 min under visible light radiation in the absence of additional oxidizing agents. Conversely, phenolic compounds suc has phenol, p-chlorophenol and p-nitrophenol are photocat- alytically degraded in approximately 3hwith additional H2O2 when irradiated with visible light. These reactions offer potentially energy effective pathways for the removal of recalcitrant organic waste contaminants.

Crowning of dibenzosilole with a naphthalenediimide functional group to prepare an electron acceptor for organic solar cells

A novel, solution-processable non-fullerene electron acceptor 9,9′-(5,5-dioctyl-5H-dibenzo [b,d]silole-3,7-diyl)bis(2,7-dioctyl-4-(octylamino)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone) (B3) based on dibenzosilole and naphthalenediimide building blocks was designed, synthesized, characterized and successfully used in a bulk-heterojunction organic solar cell. B3 displayed excellent solubility, thermal stability and acquired electron energy levels matching with those of archetypal donor polymer poly(3-hexylthiophene). Solution-processable bulk-heterojunction devices afforded 1.16% power conversion efficiency with a high fill factor of 53%. B3 is the first example in the literature using this design principle, where mild donor units at the peripheries of end-capped naphthalenediimide units tune solubility and optical energy levels simultaneously.

Novel ruthenium bipyridyl dyes with s-donor ligands and their application in dye-sensitized solar cells

Two series of novel ruthenium bipyridyl dyes incorporating sulfur-donor bidentate ligands with general formula \[Ru(R-bpy)2C2N2S2] and \[Ru(R-bpy)2(S2COEt)]\[NO3] (where R =H, CO2Et, CO2H; C2N2S2 = cyanodithioimidocarbonate and S2COEt = ethyl xanthogenate) have been synthesized and characterized spectroscopically, electrochemically and computationally. The acid derivatives in both series (C2N2S2 3 and S2COEt 6) were used as a photosensitizer in a dye-sensitized solar cell (DSSC) and the incident photo-to-current conversion efficiency (IPCE), overall efficiency (_) and kinetics of the dye/TiO2 system were investigated. It was found that 6 gave a higher efficiency cell than 3 despite the latter dye’s more favorable electronic properties, such as greater absorption range, higher molar extinction coefficient and large degree of delocalization of the HOMO. The transient absorption spectroscopy studies revealed that the recombination kinetics of 3 were unexpectedly fast, which was attributed to the terminal CN on the ligand binding to the TiO2, as evidenced by an absorption study of R =H and CO2Et dyes sensitized on TiO2, and hence leading to a lower efficiency DSSC.

Advances in heterogeneous photocatalytic degradation of phenols and dyes in wastewater : a review

The heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works in the field of photocatalytic oxidation of toxic organic compounds such as phenols and dyes, predominant in waste water effluent. In this review, the effects of various operating parameters on the photocatalytic degradation of phenols and dyes are presented. Recent findings suggested that different parameters, such as type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, mode of catalyst application, and calcinations temperature can play an important role on the photocatlytic degradation of organic compounds in water environment. Extensive research has focused on the enhancement of photocatalysis by modification of TiO2 employing metal, non-metal and ion doping. Recent advances in TiO2 photocatalysis for the degradation of various phenols and dyes are also highlighted in this review.

Proton-transfer versus nontransfer in compounds of the diazo-dye precursor 4-(phenyldiazenyl) aniline (aniline yellow) with strong organic acids: the 5-sulfosalicylate and the dichroic benzenesulfonate salts, and the 1:2 adduct with 3,5-dinitrobenzoic

The structures of two 1:1 proton-transfer red-black dye compounds formed by reaction of aniline yellow [4-(phenyldiazenyl)aniline] with 5-sulfosalicylic acid and benzenesulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitrobenzoic acid have been determined at either 130 or 200 K. The compounds are 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C12H12N3+.C7H5O6S-.CH3OH (I), 2-(4-aminophenyl)-1-hydrazin-1-ium 4-(phenydiazinyl)anilinium bis(benzenesulfonate), 2C12H12N3+.2C6H5O3S-, (II) and 4-(phenyldiazenyl)aniline-3,5-dinitrobenzoic acid (1/2) C12H11N3.2C~7~H~4~N~2~O~6~, (III). In compound (I) the diaxenyl rather than the aniline group of aniline yellow is protonated and this group subsequently akes part in a primary hydrogen-bonding interaction with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation-anion association involving aromatic C--H...O hydrogen bonds, giving a conjoint R1/2(6)R1/2(7)R2/1(4)motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and thee, together with other associations give a one-dimensional chain structure. In compound (III), rather than proton-transfer, there is a preferential formation of a classic R2/2(8) cyclic head-to-head hydrogen-bonded carboxylic acid homodimer between the two 3,5-dinitrobenzoic acid molecules, which in association with the aniline yellow molecule that is disordered across a crystallographic inversion centre, result in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzenesulfonate compound.

Fast hole surface conduction observed for indoline sensitizer dyes immobilized at fluorine-doped tin oxide - TiO2 surfaces

The indoline dyes D102, D131, D149, and D205 have been characterized when adsorved on fluorine-doped tin oxide (FTO) and TiO2 electrode surfaces. Adsorption from 50:50 acetonitrile - tert-butanol onto flourine-doped tin oxide (FTO) allows approximate Langmuirian binding constants of 6.5 x 10(4), 2.01 x 10(3), 2.0 x 10(4), and 1.5 x 10(4) mol-1 dm3, respectively, to be determined. Voltammetric data obtained in acetonitrile/0.1 M NBu4PF6 indicate reversible on-electron oxidation at Emid = 0.94, 0.91, 0.88, and 0.88 V vs Ag/AgCI(3 M KCI), respectively, with dye aggregation (at high coverage) causing additional peak features at more positive potentials. Slow chemical degradation processes and electron transfer catalysis for iodine oxidation were observed for all four oxidezed indolinium cations. When adsorbed onto TiO2 nanoparticle films (ca. 9nm particle diameter and ca.3/um thickness of FTO0, reversible voltammetric responses with Emid = 1.08, 1.156, 0.92 and 0.95 V vs Ag/AgCI(3 M KCI), respectively, suggest exceptionally fast hole hopping diffusion (with Dapp > 5 x 10(-9) m2 s-1) for adsorbed layers of four indoline dyes, presumably due to pie-pie stacking in surface aggregates. Slow dye degradation is shown to affect charge transport via electron hopping. Spectrelectrochemical data for the adsorbed indoline dyes on FTO-TiO2 revealed a red-shift of absorption peaks after oxidation and the presence of a strong charge transfer band in the near-IR region. The implications of the indoline dye reactivity and fast hole mobility for solar cell devices are discussed.