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.

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]aluminium(III)-tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]iron(III) (3/1)

In the title compound, [Al(C8H4F3O2S)3]3[Fe(C8H4F3O2S)3], the metal centre is statistically occupied by AlIII and FeIII cations in a 3:1 ratio. The metal centre is within an octahedral O6 donor set defined by three chelating substituted acetoacetonate anions. The ligands are arranged around the periphery of the molecule with a mer geometry of the S atoms.

Similarity not favourability : the role of donor prototypes in predicting willingness to donate organs while living

Using an extended Prototype/Willingness Model, we examined the predictors of willingness to donate an organ to a partner/family member and a stranger while living. A questionnaire assessed university students’ (N = 284) attitudes, subjective norm, prototype favourability, prototype similarity, moral norm, and willingness to donate organs in each recipient scenario. All variables, except prototype favourability, predicted willingness to donate organs in both situations. Future strategies should emphasise perceived approval from important others for living donation, the consistency of living donation with one’s own morals, and encourage perceptions of similarity between oneself and living donors to increase acceptance of living donation.

Knowing a donor and identifying as one : determinants of people's willingness for related and anonymous living donation in Australia

While LRD (living donation to a genetically/emotionally related recipient) is well established in Australia, LAD (living anonymous donation to a stranger) is rare. Given the increasing use of LAD overseas, Australia may likely follow suit. Understanding the determinants of people’s willingness for LAD is essential but infrequently studied in Australia. Consequently, we compared the determinants of people’s LRD and LAD willingness, and assessed whether these determinants differed according to type of living donation. We surveyed 487 health students about their LRD and LAD willingness, attitudes, identity, prior experience with blood and organ donation, deceased donation preference, and demographics. We used Structural Equation Modelling (SEM) to identify the determinants of willingness for LRD and LAD and paired sample t-tests to examine differences in LRD and LAD attitudes, identity, and willingness. Mean differences in willingness (LRD 5.93, LAD 3.92), attitudes (LRD 6.43, LAD 5.53), and identity (LRD 5.69, LAD 3.58) were statistically significant. Revised SEM models provided a good fit to the data (LRD: x2 (41) = 67.67, p = 0.005, CFI = 0.96, RMSEA = 0.04; LAD: x2 (40) = 79.64, p < 0.001, CFI = 0.95, RMSEA = 0.05) and explained 45% and 54% of the variation in LRD and LAD willingness, respectively. Four common determinants of LRD and LAD willingness emerged: identity, attitude, past blood donation, and knowing a deceased donor. Religious affiliation and deceased donation preference predicted LAD willingness also. Identifying similarities and differences in these determinants can inform future efforts aimed at understanding people’s LRD and LAD willingness and the evaluation of potential living donor motives. Notably, this study highlights the importance of people’s identification as a living donor as a motive underlying their willingness to donate their organs while living.

Disclosing donation decisions : the role of organ donor prototypes in an extended theory of planned behaviour

This study explored the role of donor prototype evaluations (perceptions of the typical organ donor) in organ donation communication decisions using an extended theory of planned behaviour (TPB) model. The model incorporated attitude, subjective norm, perceived behavioural control, moral norm, self-identity, and donor prototype evaluations to predict intentions to record consent on an organ donor register and discuss the organ donation decision with significant others. Participants completed surveys assessing the extended TPB constructs related to registering (n = 359) and discussing (n = 282). Results supported a role for donor prototype evaluations in predicting discussing intentions only. Both extended TPB structural equation models were a good fit to the data, accounting for 74 and 76% of the variance in registering and discussing intentions, respectively. Participants’ self-reported discussing behaviour (but not registering behaviour given low numbers of behavioural performers) was assessed 4 weeks later, with discussing intention as the only significant predictor of behaviour (Nagelkerke R2 = 0.11). These findings highlight the impact of people's perceptions of a typical donor on their decisions to discuss their organ donation preference, assisting our understanding of the factors influencing individuals' communication processes in efforts to bridge the gap between organ supply and demand.

Listening to late discovery adoption and donor offspring stories : adoption, ethics and implications for contemporary donor insemination practices

For most of the 20th Century a ‘closed’ system of adoption was practised throughout Australia and other modern Western societies. This ‘closed’ system was characterised by sealed records; amended birth certificates to conceal the adoption, and prohibited contact with all biological family. Despite claims that these measures protected these children from the taint of illegitimacy the central motivations were far more complex, involving a desire to protect couples from the stigma of infertility and to provide a socially acceptable family structure (Triseliotis, Feast, & Kyle, 2005; Marshall & McDonald, 2001). From the 1960s significant evidence began to emerge that many adopted children and adults were experiencing higher incidences of psychological difficulties, characterised by problems with psychological adjustment, building self-esteem and forming a secure personal identity. These difficulties became grouped under the term ‘genealogical bewilderment’. As a result, new policies and practices were introduced to try to place the best interests of the child at the forefront. These changes reflected new understandings of adoption; as not only an individual process but also as a social and relational process that continues throughout life. Secrecy and the withholding of birth information are now prohibited in the overwhelming majority of all domestic adoptions processed in Australia (Marshall & McDonald, 2001). One little known consequence of this ‘closed’ system of adoption was the significant number of children who were never told of their adoptive status. As a consequence, some have discovered or had this information disclosed to them, as adults. The first study that looked at the late discovery of genetic origins experiences was conducted by the Post Adoption Resource Centre in New South Wales in 1999. This report found that the participants in their study expressed feelings of disbelief, confusion, anger, sorrow and loss. Further, the majority of participants continued to struggle with issues arising from this intentional concealment of their genetic origins (Perl & Markham, 1999). A second and more recent study (Passmore, Feeney & Foulstone, 2007) looked at the issue of secrecy in adoptive families as part of a broader study of 144 adult adoptees. This study found that secrecy and/or lies or misinformation on the part of adoptive parents had negative effects on both personal identity and relationships with others. The authors noted that those adoptees who found out about their adoption as adults were ‘especially likely to feel a sense of betrayal’ (p.4). Over recent years, stories of secrecy and late discovery have also started to emerge from sperm donor conceived adults (Spencer, 2007; Turner & Coyle, 2000). Current research evidence shows that although a majority of couples during the donor assisted conception process indicate that they intend to tell the offspring about their origins, as many as two-thirds or more of couples continue to withhold this information from their children (Akker, 2006; Gottlieb, A. McWhinnie, 2001; Salter-Ling, Hunter, & Glover, 2001). Why do they keep this secret? Infertility involves a range of complex factors that are often left unresolved or poorly understood by those choosing insemination by donor as a form of family building (Schaffer, J. A., & Diamond, R., 1993). These factors may only impact after the child is born, when resemblance talk becomes most pronounced. Resemblance talk is an accepted form of public discourse and a social convention that legitimises the child as part of the family and is part of the process of constructing the child’s identity within the family. Couples tend to become focused on resemblance as this is where they feel most vulnerable, and the lack of resemblance to the parenting father may trigger his sense of loss (Becker, Butler, & Nachtigall, 2005).

Modulation of dermal microvascular endithelial cell responses to growth factors and haemostatic factors in the presence of vitronectin

In order to effect permanent closure in burns patients suffering from full thickness wounds, replacing their skin via split thickness autografting, is essential. Dermal substitutes in conjunction with widely meshed split thickness autografts (+/- cultured keratinocytes) reduce scarring at the donor and recipient sites of burns patients by reducing demand for autologous skin (both surface area and thickness), without compromising dermal delivery at the wound face. Tissue engineered products such as Integra consist of a dermal template which is rapidly remodelled to form a neodermis, at which time the temporary silicone outer layer is removed and replaced with autologous split thickness skin. Whilst provision of a thick tissue engineered dermis at full thickness burn sites reduces scarring, it is hampered by delays in vascularisation which results in clinical failure. The ultimate success of any skin graft product is dependent upon a number of basic factors including adherence, haemostasis and in the case of viable tissue grafts, success is ultimately dependent upon restoration of a normal blood supply, and hence this study. Ultimately, the goal of this research is to improve the therapeutic properties of tissue replacements, through impregnation with growth factors aimed at stimulating migration and proliferation of microvascular endothelial cells into the donor tissue post grafting. For the purpose of my masters, the aim was to evaluate the responsiveness of a dermal microvascular endothelial cell line to growth factors and haemostatic factors, in the presence of the glycoprotein vitronectin. Vitronectin formed the backbone for my hypothesis and research due to its association with both epithelial and, more specifically, endothelial migration and proliferation. Early work using a platform technology referred to as VitroGro (Tissue Therapies Ltd), which is comprised of vitronectin bound BP5/IGF-1, aided keratinocyte proliferation. I hypothesised that this result would translate to another epithelium - endothelium. VitroGro had no effect on endothelial proliferation or migration. Vitronectin increases the presence of Fibroblast Growth Factor (FGF) and Vascular Endothelial Growth Factor (VEGF) receptors, enhancing cell responsiveness to their respective ligands. So, although Human Microvascular Endothelial Cell line 1 (HMEC-1) VEGF receptor expression is generally low, it was hypothesised that exposure to vitronectin would up-regulate this receptor. HMEC-1 migration, but not proliferation, was enhanced by vitronectin bound VEGF, as well as vitronectin bound Epidermal Growth Factor (EGF), both of which could be used to stimulate microvascular endothelial cell migration for the purpose of transplantation. In addition to vitronectin's synergy with various growth factors, it has also been shown to play a role in haemostasis. Vitronectin binds thrombin-antithrombin III (TAT) to form a trimeric complex that takes on many of the attributes of vitronectin, such as heparin affinity, which results in its adherence to endothelium via heparan sulfate proteoglycans (HSP), followed by unaltered transcytosis through the endothelium, and ultimately its removal from the circulation. This has been documented as a mechanism designed to remove thrombin from the circulation. Equally, it could be argued that it is a mechanism for delivering vitronectin to the matrix. My results show that matrix-bound vitronectin dramatically alters the effect that conformationally altered antithrombin three (cATIII) has on proliferation of microvascular endothelial cells. cATIII stimulates HMEC-1 proliferation in the presence of matrix-bound vitronectin, as opposed to inhibiting proliferation in its absence. Binding vitronectin to tissues and organs prior to transplant, in the presence of cATIII, will have a profound effect on microvascular infiltration of the graft, by preventing occlusion of existing vessels whilst stimulating migration and proliferation of endothelium within the tissue.

catena-Poly[[[diaquacobalt(II)]-mu-(3,5-dinitro-2-oxidobenzoato)-kappa3O1,O2:O1'-[tetraaquacobalt(II)]-mu-(3,5-dinitro-2-oxidobenzoato)-kappa3-O1:O1',O2] dihydrate]

In the structure of polymeric title compound, {[Co2(C7H2N2O7)2(H2O)6] . 2H2O}n from the reaction of 3,5-dinitrosalicylic acid with cobalt(II) acetate, both slightly distorted octahedral Co(II) centres have crystallographic inversion symmetry. The coordination sphere about one Co centre comprises four O donors from two bidentate chelate O(phenolate), O(carboxyl) and bridging dianionic ligands and two water molecules [Co-O range, 2.0249(11)-2.1386(14)A] while that about the second Co centre has four water molecules and two bridging carboxyl O donor atoms [Co-O range, 2.0690(14)-2.1364(11)A]. The coordinated water molecules as well as the water molecules of solvation give water-water and water-carboxyl hydrogen-bonding interactions in the three-dimensional framework structure.

A Transformational Role : Donor and charity perspectives on major giving in Australia

Tapping into the thoughts of nearly 50 Australians involved with major giving, this study seeks to know more about why and how people give in what might be called ‘momentous’ ways. It tracks both their triumphs and trials. Perhaps most importantly, it gives a public voice to the perceptions, attitudes, concerns and stories of Australians who have chosen to act philanthropically in a sizeable and ongoing way. In counterpoint, the views, experiences and frustrations of seasoned fundraising professionals who work to generate major giving across a range of causes form the other voices in this study. Thus, donors talk about giving, and occasionally raising support from their peers, and fundraisers talk about developing major gifts. This research has been supported by the Perpetual Foundation, the EF and SL Gluyas Trust and the Edward Corbould Charitable Trust under the management of Perpetual Trustee Company Ltd.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.