Photocatalytic hydrogen production with iron oxide under solar irradiation

As solar hydrogen is a sustainable and environmental friendly energy carrier, it is considered to take the place of fossil fuels in the near future. Solar hydrogen can be generated by splitting of water under solar light illumination. In this study, the use of nanostructured hematite thin-film electrodes in photocatalytic water splitting was investigated. Hematite (á-Fe2O3) has a narrow band-gap of 2.2 eV, which is able to utilise approximately 40% of solar radiation. However, poor photoelectrochemical performance is observed for hematite due to low electrical conductivity and a high rate of electron-hole recombination. An extensive review of useful measures taken to overcoming the disadvantages of hematite so as to enhance its performance was presented including thin-film structure, nanostructuring, doping, etc. Since semiconductoring materials which exhibit an inverse opal structure are expected to have a high surface-volume ratio, unique optical characteristics and a shorter distance for photogenerated holes to travel to the electrode/electrolyte interface, inverse opals of hematite thin films deposited on FTO glass substrate were successfully prepared by doctor blading using PMMA as a template. However, due to the poor adhesion of the films, an acidic medium (i.e., 2 M HCl) was employed to significantly enhance the adhesion of the films, which completely destroyed the inverse opal structure. Therefore, undoped, Ti and Zn-doped hematite thin films deposied on FTO glass substrate without an inverse opal structure were prepared by doctor blading and spray pyrolysis and characterised using SEM, EDX, XRD, TGA, UV-Vis spectroscopy and photoelectrochemical measurements. Regarding the doped hematite thin films prepared by doctor blading, the photoelectrochemical activity of the hematite photoelectrodes was improved by incorporation of Ti, most likely owing to the increased electrical conductivity of the films, the stabilisation of oxygen vacancies by Ti4+ ions and the increased electric field of the space charge layer. A highest photoresponse was recorded in case of 2.5 at.% Ti which seemed to be an optimal concentration. The effect of doping content, thickness, and calcination temperature on the performance of the Ti-doped photoelectrodes was investigated. Also, the photoactivity of the 2.5 at.% Ti-doped samples was examined in two different types of electrochemical cells. Zn doping did not enhance the photoactivity of the hematite thin films though Zn seemed to enhance the hole transport due to the slow hole mobility of hematite which could not be overcome by the enhancement. The poor performance was also obtained for the Ti-doped samples prepared by spray pyrolysis, which appeared to be a result of introduction of impurities from the metallic parts of the spray gun in an acidic medium. Further characterisation of the thin-film electrodes is required to explain the mechanism by which enhanced performance was obtained for Ti-doped electrodes (doctor blading) and poor photoactivity for Zn and Ti-doped samples which were synthesised by doctor blading and spray pyrolysis, respectively. Ti-doped hematite thin films will be synthesised in another way, such as dip coating so as to maintain an inverse opal structure as well as well adhesion. Also, a comparative study of the films will be carried out.

Evaluating the success of large-scale, integrated information systems through the lens of IS-impact and IS-support

This study proceeds from a central interest in the importance of systematically evaluating operational large-scale integrated information systems (IS) in organisations. The study is conducted within the IS-Impact Research Track at Queensland University of Technology (QUT). The goal of the IS-Impact Track is, "to develop the most widely employed model for benchmarking information systems in organizations for the joint benefit of both research and practice" (Gable et al, 2009). The track espouses programmatic research having the principles of incrementalism, tenacity, holism and generalisability through replication and extension research strategies. Track efforts have yielded the bicameral IS-Impact measurement model; the ‘impact’ half includes Organisational-Impact and Individual-Impact dimensions; the ‘quality’ half includes System-Quality and Information-Quality dimensions. Akin to Gregor’s (2006) analytic theory, the ISImpact model is conceptualised as a formative, multidimensional index and is defined as "a measure at a point in time, of the stream of net benefits from the IS, to date and anticipated, as perceived by all key-user-groups" (Gable et al., 2008, p: 381). The study adopts the IS-Impact model (Gable, et al., 2008) as its core theory base. Prior work within the IS-Impact track has been consciously constrained to Financial IS for their homogeneity. This study adopts a context-extension strategy (Berthon et al., 2002) with the aim "to further validate and extend the IS-Impact measurement model in a new context - i.e. a different IS - Human Resources (HR)". The overarching research question is: "How can the impacts of large-scale integrated HR applications be effectively and efficiently benchmarked?" This managerial question (Cooper & Emory, 1995) decomposes into two more specific research questions – In the new HR context: (RQ1): "Is the IS-Impact model complete?" (RQ2): "Is the ISImpact model valid as a 1st-order formative, 2nd-order formative multidimensional construct?" The study adhered to the two-phase approach of Gable et al. (2008) to hypothesise and validate a measurement model. The initial ‘exploratory phase’ employed a zero base qualitative approach to re-instantiating the IS-Impact model in the HR context. The subsequent ‘confirmatory phase’ sought to validate the resultant hypothesised measurement model against newly gathered quantitative data. The unit of analysis for the study is the application, ‘ALESCO’, an integrated large-scale HR application implemented at Queensland University of Technology (QUT), a large Australian university (with approximately 40,000 students and 5000 staff). Target respondents of both study phases were ALESCO key-user-groups: strategic users, management users, operational users and technical users, who directly use ALESCO or its outputs. An open-ended, qualitative survey was employed in the exploratory phase, with the objective of exploring the completeness and applicability of the IS-Impact model’s dimensions and measures in the new context, and to conceptualise any resultant model changes to be operationalised in the confirmatory phase. Responses from 134 ALESCO users to the main survey question, "What do you consider have been the impacts of the ALESCO (HR) system in your division/department since its implementation?" were decomposed into 425 ‘impact citations.’ Citation mapping using a deductive (top-down) content analysis approach instantiated all dimensions and measures of the IS-Impact model, evidencing its content validity in the new context. Seeking to probe additional (perhaps negative) impacts; the survey included the additional open question "In your opinion, what can be done better to improve the ALESCO (HR) system?" Responses to this question decomposed into a further 107 citations which in the main did not map to IS-Impact, but rather coalesced around the concept of IS-Support. Deductively drawing from relevant literature, and working inductively from the unmapped citations, the new ‘IS-Support’ construct, including the four formative dimensions (i) training, (ii) documentation, (iii) assistance, and (iv) authorisation (each having reflective measures), was defined as: "a measure at a point in time, of the support, the [HR] information system key-user groups receive to increase their capabilities in utilising the system." Thus, a further goal of the study became validation of the IS-Support construct, suggesting the research question (RQ3): "Is IS-Support valid as a 1st-order reflective, 2nd-order formative multidimensional construct?" With the aim of validating IS-Impact within its nomological net (identification through structural relations), as in prior work, Satisfaction was hypothesised as its immediate consequence. The IS-Support construct having derived from a question intended to probe IS-Impacts, too was hypothesised as antecedent to Satisfaction, thereby suggesting the research question (RQ4): "What is the relative contribution of IS-Impact and IS-Support to Satisfaction?" With the goal of testing the above research questions, IS-Impact, IS-Support and Satisfaction were operationalised in a quantitative survey instrument. Partial least squares (PLS) structural equation modelling employing 221 valid responses largely evidenced the validity of the commencing IS-Impact model in the HR context. ISSupport too was validated as operationalised (including 11 reflective measures of its 4 formative dimensions). IS-Support alone explained 36% of Satisfaction; IS-Impact alone 70%; in combination both explaining 71% with virtually all influence of ISSupport subsumed by IS-Impact. Key study contributions to research include: (1) validation of IS-Impact in the HR context, (2) validation of a newly conceptualised IS-Support construct as important antecedent of Satisfaction, and (3) validation of the redundancy of IS-Support when gauging IS-Impact. The study also makes valuable contributions to practice, the research track and the sponsoring organisation.

Targeted flight opportunities with large area collectors

A major factor in the stratospheric collection process is the relative density of particles at the collection altitude. With current aircraft-borne collector plate geometries, one potential extraterrestrial particle of about 10 micron diameter is collected approximately every hour. However, a new design for the collector plate, termed the Large Area Collector (LAC), allows a factor of 10 improvement in collection efficiency over current conventional geometry. The implementation of LAC design on future stratospheric collection flights will provide many opportunities for additional data on both terrestrial and extraterrestrial phenomena. With the improvement in collection efficiency, LAC's may provide a suitable number of potential extraterrestrial particles in one short flight of between 4 and 8 hours duration. Alternatively, total collection periods of approximately 40 hours enhance the probability that rare particles can be retrieved from the stratosphere. This latter approach is of great value for the cosmochemist who may wish to perform sophisticated analyses on interplanetary dust greater than a picogram. The former approach, involving short duration flights, may also provide invaluable data on the source of many extraterrestrial particles. The time dependence of particle entry to the collection altitude is an important parameter which may be correlated with specific global events (e.g., meteoroid streams) provided the collection time is known to an accuracy of 2 hours.

Effect of aerobic interval training and caffeine on blood platelet function

Purpose: Hyperactive platelets contribute to the thrombotic response in humans, and exercise transiently increases platelet function. Caffeine is routinely used by athletes as an ergogenic aid, but the combined effect of exercise and caffeine on platelet function has not been investigated. Methods: Twelve healthy males were randomly assigned to one of four groups and undertook four experimental trials of a high-intensity aerobic interval training (AIT) bout or rest with ingestion of caffeine (3 mg·kg-1) or placebo. AIT was 8 × 5 min at approximately 75% peak power output (approximately 80% V?O2peak) and 1-min recovery (approximately 40% peak power output, approximately 50% V?O2peak) intervals. Blood/urine was collected before, 60, and 90 min after capsule ingestion and analyzed for platelet aggregation/activation. Results: AIT increased platelet reactivity to adenosine diphosphate (placebo 30.3%, caffeine 13.4%, P < 0.05) and collagen (placebo 10.8%, caffeine 5.1%, P < 0.05) compared with rest. Exercise placebo increased adenosine diphosphate-induced aggregation 90 min postingestion compared with baseline (40.5%, P < 0.05), but the increase when exercise was combined with caffeine was small (6.6%). During the resting caffeine protocol, collagen-induced aggregation was reduced (-4.3%, P < 0.05). AIT increased expression of platelet activation marker PAC-1 with exercise placebo (P < 0.05) but not when combined with caffeine. Conclusion: A single bout of AIT increases platelet function, but caffeine ingestion (3 mg·kg) does not exacerbate platelet function at rest or in response to AIT. Our results provide new information showing caffeine at a dose that can elicit ergogenic effects on performance has no detrimental effect on platelet function and may have the potential to attenuate increases in platelet activation and aggregation when undertaking strenuous exercise.

Bone-anchored prosthesis: Current developments worldwide and challenges

Background Individuals with limb amputation fitted with conventional socket-suspended prostheses often experience socket related discomfort leading to a significant decrease in quality of life. Most of these concerns can be overcome by surgical techniques enabling bone-anchored prostheses. In this case, the prosthesis is attached directly to the residual skeleton through a percutaneous implant (e.g., screw type fixation, press-fit implant).[46, 48, 51, 52, 77, 78] The aim of this study is to present the current advances in these surgical techniques worldwide with a strong focus on the current challenges. Methods The current advances will be extracted from a systematic literature review including approximately 40 articles. The outcomes measured will include the estimation of the population worldwide as well as the complications (e.g., infection, loosening, fractures, and breakage) and the benefits (e.g., functional outcomes, health-related quality of life).[5-19, 51-53, 55, 57, 58, 62, 73, 79] Results The population of individuals fitted with a bone-anchored prosthesis is approximately 550 worldwide. Publications focusing on infection are sparse. However, the rate of superficial infection is estimated at 20%. Deep infection occurs rarely. Loosening and peri-prosthetic fractures are fairly uncommon. Breakage of implant parts occurs regularly mainly due to fall. All studies reported a significant improvement in functional level and overall quality of life. Conclusions Several commercial implants are in developments in Europe and US. The number of procedures is consistently growing worldwide. This technique might be primary way to fit a prosthesis to young and active amputees by 2025.

Bone-anchored prosthesis: Current developments worldwide and challenges

Background Individuals with limb amputation fitted with conventional socket-suspended prostheses often experience socket related discomfort leading to a significant decrease in quality of life. Most of these concerns can be overcome by surgical techniques enabling bone-anchored prostheses. In this case, the prosthesis is attached directly to the residual skeleton through a percutaneous implant (e.g., screw type fixation, press-fit implant).[46, 48, 51, 52, 77, 78] The aim of this study is to present the current advances in these surgical techniques worldwide with a strong focus on the current challenges. Methods The current advances will be extracted from a systematic literature review including approximately 40 articles. The outcomes measured will include the estimation of the population worldwide as well as the complications (e.g., infection, loosening, fractures, and breakage) and the benefits (e.g., functional outcomes, health-related quality of life).[5-19, 51-53, 55, 57, 58, 62, 73, 79] Results The population of individuals fitted with a bone-anchored prosthesis is approximately 550 worldwide. Publications focusing on infection are sparse. However, the rate of superficial infection is estimated at 20%. Deep infection occurs rarely. Loosening and peri-prosthetic fractures are fairly uncommon. Breakage of implant parts occurs regularly mainly due to fall. All studies reported a significant improvement in functional level and overall quality of life. Conclusions Several commercial implants are in developments in Europe and US. The number of procedures is consistently growing worldwide. This technique might be primary way to fit a prosthesis to young and active amputees by 2025.

The performance of irrigated mixtures of tall fescue, ryegrass and white clover in subtropical Australia. 1. The effects of sowing mixture combinations, nitrogen and oversowing on establishment, productivity, botanical composition and persistence.

In the subtropics of Australia, the ryegrass component of irrigated perennial ryegrass (Lolium perenne) - white clover (Trifolium repens) pastures declines by approximately 40% in the summer following establishment, being replaced by summer-active C4 grasses. Tall fescue (Festuca arundinacea) is more persistent than perennial ryegrass and might resist this invasion, although tall fescue does not compete vigorously as a seedling. This series of experiments investigated the influence of ryegrass and tall fescue genotype, sowing time and sowing mixture as a means of improving tall fescue establishment and the productivity and persistence of tall fescue, ryegrass and white clover-based mixtures in a subtropical environment. Tall fescue frequency at the end of the establishment year decreased as the number of companion species sown in the mixture increased. Neither sowing mixture combinations nor sowing rates influenced overall pasture yield (of around 14 t/ha) in the establishment year but had a significant effect on botanical composition and component yields. Perennial ryegrass was less competitive than short-rotation ryegrass, increasing first-year yields of tall fescue by 40% in one experiment and by 10% in another but total yield was unaffected. The higher establishment-year yield (3.5 t/ha) allowed Dovey tall fescue to compete more successfully with the remaining pasture components than Vulcan (1.4 t/ha). Sowing 2 ryegrass cultivars in the mixture reduced tall fescue yields by 30% compared with a single ryegrass (1.6 t/ha), although tall fescue alone achieved higher yields (7.1 t/ha). Component sowing rate had little influence on composition or yield. Oversowing the ryegrass component into a 6-week-old sward of tall fescue and white clover improved tall fescue, white clover and overall yields in the establishment year by 83, 17 and 11%, respectively, but reduced ryegrass yields by 40%. The inclusion of red (T. pratense) and Persian (T. resupinatum) clovers and chicory (Cichorium intybus) increased first-year yields by 25% but suppressed perennial grass and clover components. Yields were generally maintained at around 12 t/ha/yr in the second and third years, with tall fescue becoming dominant in all 3 experiments. The lower tall fescue seeding rate used in the first experiment resulted in tall fescue dominance in the second year following establishment, whereas in Experiments 2 and 3 dominance occurred by the end of the first year. Invasion by the C4 grasses was relatively minor (<10%) even in the third year. As ryegrass plants died, tall fescue and, to a lesser extent, white clover increased as a proportion of the total sward. Treatment effects continued into the second, but rarely the third, year and mostly affected the yield of one of the components rather than total cumulative yield. Once tall fescue became dominant, it was difficult to re-introduce other pasture components, even following removal of foliage and moderate renovation. Severe renovation (reducing the tall fescue population by at least 30%) seems a possible option for redressing this situation.

Physical activity in mid-age and older women: Lessons from the Australian longitudinal study on women’s health

The Australian Longitudinal Study on Women’s Health (ALSWH) commenced in Australia in 1996 when researchers recruited approximately 40,000 women in three birth cohorts: 1973–1978, 1946–1951, and 1921–1926. Since then participants have completed surveys on a wide range of health issues, at approximately three-year intervals. This overview describes changes in physical activity (PA) over time in the mid-age and older ALSWH cohorts, and summarizes the findings of studies published to date on the determinants of PA, and its associated health outcomes in Australian women. The ALSWH data show a significant increase in PA during mid-age, and a rapid decline in activity levels when women are in their 80s. The study has demonstrated the importance of life stages and key life events as determinants of activity, the additional benefits of vigorous activity for mid-age women, and the health benefits of ‘only walking’ for older women. ALSWH researchers have also drawn attention to the benefits of activity in terms of a wide range of physical and mental health outcomes, as well as overall vitality and well-being. The data indicate that maintaining a high level of PA throughout mid and older age will not only reduce the risk of premature death, but also significantly extend the number of years of healthy life.

The effect of ongoing blood loss on human serum concentrations of perfluorinated acids

Perfluorinated alkyl acids (PFAAs) have been detected in serum at low concentrations in background populations. Higher concentrations haven been observed in adult males compared to females, with a possible explanation that menstruation offers females an additional elimination route. In this study, we examined the significance of blood loss as an elimination route of PFAAs. Pooled serum samples were collected from individuals undergoing a medical procedure involving ongoing blood withdrawal called venesection. Concentrations from male venesection patients were approximately 40% lower than males in the general population for perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). A simple pharmacokinetic model was used to test the hypothesis that blood loss could explain why adult males have higher concentrations of PFAAs than females, and why males undergoing venesections had lower concentrations compared to males in the general population. The model application generally supported these hypotheses showing that venesection might reduce blood serum concentrations by 37% (PFOA) and 53% (PFOS) compared to the observed difference of 44% and 37%. Menstruation was modeled to show a 22% reduction in PFOA serum concentrations compared to a 24% difference in concentrations between males and females in the background population. Uncertainties in the modeling and the data are identified and discussed.

Effects of large-scale human land use on Capercaillie (Tetrao urogallus L.) populations in Finland

The Capercaillie (Tetrao urogallus L.) is often used as a focal species for landscape ecological studies: the minimum size for its lekking area is 300 ha, and the annual home range for an individual may cover 30 80 km2. In Finland, Capercaillie populations have decreased by approximately 40 85%, with the declines likely to have started in the 1940s. Although the declines have partly stabilized from the 1990s onwards, it is obvious that the negative population trend was at least partly caused by changes in human land use. The aim of this thesis was to study the connections between human land use and Capercaillie populations in Finland, using several spatial and temporal scales. First, the effect of forest age structure on Capercaillie population trends was studied in 18 forestry board districts in Finland, during 1965 1988. Second, the abundances of Capercaillie and Moose (Alces alces L.) were compared in terms of several land-use variables on a scale of 50 × 50 km grids and in five regions in Finland. Third, the effects of forest cover and fine-grain forest fragmentation on Capercaillie lekking area persistence were studied in three study locations in Finland, on 1000 and 3000 m spatial scales surrounding the leks. The analyses considering lekking areas were performed with two definitions for forest: > 60 and > 152 m3ha 1 of timber volume. The results show that patterns and processes at large spatial scales strongly influence Capercaillie in Finland. In particular, in southwestern and eastern Finland, high forest cover and low human impact were found to be beneficial for this species. Forest cover (> 60 m3ha 1 of timber) surrounding the lekking sites positively affected lekking area persistence only at the larger landscape scale (3000 m radius). The effects of older forest classes were hard to assess due to scarcity of older forests in several study areas. Young and middle-aged forest classes were common in the vicinity of areas with high Capercaillie abundances especially in northern Finland. The increase in the amount of younger forest classes did not provide a good explanation for Capercaillie population decline in 1965 1988. In addition, there was no significant connection between mature forests (> 152 m3ha 1 of timber) and lekking area persistence in Finland. It seems that in present-day Finnish landscapes, area covered with old forest is either too scarce to efficiently explain the abundance of Capercaillie and the persistence of the lekking areas, or the effect of forest age is only important when considering smaller spatial scales than the ones studied in this thesis. In conclusion, larger spatial scales should be considered for assessing the future Capercaillie management. According to the proposed multi-level planning, the first priority should be to secure the large, regional-scale forest cover, and the second priority should be to maintain fine-grained, heterogeneous structure within the separate forest patches. A management unit covering hundreds of hectares, or even tens or hundreds of square kilometers, should be covered, which requires regional-level land-use planning and co-operation between forest owners.

Agricultural expansion and climate change in the Taita Hills, Kenya: an assessment of potential environmental impacts

The indigenous cloud forests in the Taita Hills have suffered substantial degradation for several centuries due to agricultural expansion. Currently, only 1% of the original forested area remains preserved in this region. Furthermore, climate change imposes an imminent threat for local economy and environmental sustainability. In such circumstances, elaborating tools to conciliate socioeconomic growth and natural resources conservation is an enormous challenge. This dissertation tackles essential aspects for understanding the ongoing agricultural activities in the Taita Hills and their potential environmental consequences in the future. Initially, alternative methods were designed to improve our understanding of the ongoing agricultural activities. Namely, methods for agricultural survey planning and to estimate evapotranspiration were evaluated, taking into account a number of limitations regarding data and resources availability. Next, this dissertation evaluates how upcoming agricultural expansion, together with climate change, will affect the natural resources in the Taita Hills up to the year 2030. The driving forces of agricultural expansion in the region were identified as aiming to delineate future landscape scenarios and evaluate potential impacts from the soil and water conservation point of view. In order to investigate these issues and answer the research questions, this dissertation combined state of the art modelling tools with renowned statistical methods. The results indicate that, if current trends persist, agricultural areas will occupy roughly 60% of the study area by 2030. Although the simulated land use changes will certainly increase soil erosion figures, new croplands are likely to come up predominantly in the lowlands, which comprise areas with lower soil erosion potential. By 2030, rainfall erosivity is likely to increase during April and November due to climate change. Finally, this thesis addressed the potential impacts of agricultural expansion and climate changes on Irrigation Water Requirements (IWR), which is considered another major issue in the context of the relations between land use and climate. Although the simulations indicate that climate change will likely increase annual volumes of rainfall during the following decades, IWR will continue to increase due to agricultural expansion. By 2030, new cropland areas may cause an increase of approximately 40% in the annual volume of water necessary for irrigation.

Phase transitions in triammonium hydrogen disulphate: Crystal structure of an intermediate stable phase at-90 degrees C

Triammonium hydrogen disulphate, (NH4)(3)H(SO4)(2), belongs to the family of crystal structures M3H(XO4)(2) (with M = NH4, K, Rb, Cs, and X = S, Se) which display super protonic phases at elevated temperatures, while at room temperature these are relatively poor proton conductors. The crystal structure of triammonium hydrogen disulphate has been determined by X-ray diffraction at -90 degrees C and the variation in the characteristics of the hydrogen bond is discussed in comparison with that of the structures at -110 degrees C and room temperature. It is concluded that the mechanics involving the proton migration in such systems is realised in terms of the variations in the hydrogen bond features with temperature.

Ovarian developmental variation in the primitively eusocial wasp Ropalidia marginata suggests a gateway to worker ontogeny and the evolution of sociality

Social insects are characterized by reproductive caste differentiation of colony members into one or a small number of fertile queens and a large number of sterile workers. The evolutionary origin and maintenance of such sterile workers remains an enduring puzzle in insect sociobiology. Here, we studied ovarian development in over 600 freshly eclosed, isolated, virgin female Ropalidia marginata wasps, maintained in the laboratory. The wasps differed greatly both in the time taken to develop their ovaries and in the magnitude of ovarian development despite having similar access to resources. All females started with no ovarian development at day zero, and the percentage of individuals with at least one oocyte at any stage of development increased gradually across age, reached 100% at 100. days and decreased slightly thereafter. Approximately 40% of the females failed to develop ovaries within the average ecological lifespan of the species. Age, body size and adult feeding rate, when considered together, were the most important factors governing ovarian development. We suggest that such flexibility and variation in the potential and timing of reproductive development may physiologically predispose females to accept worker roles and thus provide a gateway to worker ontogeny and the evolution of sociality.

Depalladation of Neutral Monoalkyne- and Dialkyne-Inserted Palladacycles and Alkyne Insertion/Depalladation Reactions of Cationic Palladacycles Derived from N,N `,N `'-Triarylguanidines as Facile Routes for Guanidine-Containing Heterocycles/Carbocycles: Synthetic, Structural, and Mechanistic Aspects

Depalladation of the monoalkyne-inserted cyclopalldated guanidines (kappa 2(C,N)Pd(2,6-Me2C5H3N)Br] (I and II) in PhCl under reflux conditions and that of the dialkyne-inserted cyclopalladated guanidine kappa(2)(C,N):eta(2)(C=C)PdBr] (III) in pyridine under reflux conditions afforded a guanidine-containing indole (1), imidaziondole (2), and benzazepine (3) in 80%, 67%, and 76%, yields, respectively. trans-L2PdBr2] species (L = 2,6-Me2C5H3N, C5H5N) were also isolated in the aforementioned reactions in 35%, 42%, and 40% yields. Further , the reaction of the cyclopalladated guanidine kappa(2)(C,N)Pd(mu-Br)](2) (IV) with AgBF4 in a CH2Cl2/MeCN mixture afforded the cationic pincer type cyclopalladated guanidine kappa(3)(C,N,O)Pd(MeCN)]BF4] (4) in 85% yield and this palladacycle upon crystallization in MeCN and the reaction of kappa(2)(C,N)Pd(mu-Br)](2) (V) with AgBf(4) in a CH2Cl2/MeCN mixture afforded the cationic palladacycles {kappa(2)(C,N)Pd(MeCN)(2)]BF4](5 and 6) in 89% and 91% yields, respectively. The separate reactions of 4 with 2 equiv of methyl phenylpropiolate (MPP) or diphenylacetylene (DPA) and the reaction of 5 with 2 equiv of MPP in PhCl at 110 degrees C afforded the guanidine-containing quinazolinium tetrafluoroborate 7 in 25-32% yields. The reaction of 6 with 2 equiv of DPA under otherwise identical conditions afforded the unsymmetrically substituted guanidinium tetrafluoroborate 8, containing a highly substituted naphthalene unit, in 82% yield. Compounds 1-8 were characterized by analytical and spectroscopic techniques, and all compounds except 4 were characterized by single-crystal X-ray diffraction. The Molecular structure of 2 and 3 are nove, as the framework in the former arises due to the formation of two C-N bonds upon depalladation while the butadienyl unit in the latter revealed cis,cis stereochemistry, a-feature unprecedented in alkyne insertion chemistry. Plausible pathways for the formation of heterocycles/carbocycles are proposed. the influence of substitutents on the aryl rings fo the cyclopalladated guanidine moiety and those on alkynes upon the nature of the products in addressed. Heterocycles 1 and 7 revealed the presence of two rotamers in about a 1.00:0.43 ratio in CDCl3 and in about a 1.00:0.14 ratio in CD3OD, respectively, as detected by H-1 NMR spectroscopy while in CD3CN and DMSO-d(6) (1) and CD3CN and CDCl3 (7), these heterocycles revealed the presence of a single rotamer. These spectral features are attributed to the restricted C-N single-bond rotation of the CN3 unit of the guanidine moiety, which possibly arises from steric constraint due to the formation of a N-H center dot center dot center dot Cl hydrogen bond with CDCl3 (1) and N-H center dot center dot center dot O and O-D center dot center dot center dot O hydrogen bonds with CD3OD (7).

Comments on hydrographic and topographic LIDAR acquisition and merging with multibeam sounding data acquired in the Olympic Coast National Marine Sanctuary

In April 2005, a SHOALS 1000T LIDAR system was used as an efficient alternative for safely acquiring data to describe the existing conditions of nearshore bathymetry and the intertidal zone over an approximately 40.7 km2 (11.8 nm2) portion of hazardous coastline within the Olympic Coast National Marine Sanctuary (OCNMS). Data were logged from 1,593 km (860 nm) of track lines in just over 21 hours of flight time. Several islands and offshore rocks were also surveyed, and over 24,000 geo-referenced digital still photos were captured to assist with data cleaning and QA/QC. The 1 kHz bathymetry laser obtained a maximum water depth of 22.2 meters. Floating kelp beds, breaking surf lines and turbid water were all challenges to the survey. Although sea state was favorable for this time of the year, recent heavy rainfall and a persistent low-lying layer of fog reduced acquisition productivity. The existence of a completed VDatum model covering this same geographic region permitted the LIDAR data to be vertically transformed and merged with existing shallow water multibeam data and referenced to the mean lower low water (MLLW) tidal datum. Analysis of a multibeam bathymetry-LIDAR difference surface containing over 44,000 samples indicated surface deviations from –24.3 to 8.48 meters, with a mean difference of –0.967 meters, and standard deviation of 1.762 meters. Errors in data cleaning and false detections due to interference from surf, kelp, and turbidity likely account for the larger surface separations, while the remaining general surface difference trend could partially be attributed to a more dense data set, and shoal-biased cleaning, binning and gridding associated with the multibeam data for maintaining conservative least depths important for charting dangers to navigation. (PDF contains 27 pages.)